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Sample records for cationic intermediate stabilization

  1. Reactions of stabilized Criegee Intermediates

    Science.gov (United States)

    Vereecken, Luc; Harder, Hartwig; Novelli, Anna

    2014-05-01

    Carbonyl oxides (Criegee intermediates) were proposed as key intermediates in the gas phase ozonolysis of alkenes in 1975 by Rudolf Criegee. Despite the importance of ozonolysis in atmospheric chemistry, direct observation of these intermediates remained elusive, with only indirect experimental evidence for their role in the oxidation of hydrocarbons, e.g. through scavenging experiments. Direct experimental observation of stabilized CI has only been achieved since 2008. Since then, a concerted effort using experimental and theoretical means is in motion to characterize the chemistry and kinetics of these reactive intermediates. We present the results of theoretical investigations of the chemistry of Criegee intermediates with a series of coreactants which may be of importance in the atmosphere, in experimental setups, or both. This includes the CI+CI cross-reaction, which proceeds with a rate coefficient near the collision limit and can be important in experimental conditions. The CI + alkene reactions show strong dependence of the rate coefficient depending on the coreactants, but is generally found to be rather slow. The CI + ozone reaction is sufficiently fast to occur both in experiment and the free troposphere, and acts as a sink for CI. The reaction of CI with hydroperoxides, ROOH, is complex, and leads both to the formation of oligomers, as to the formation of reactive etheroxides, with a moderately fast rate coefficient. The importance of these reactions is placed in the context of the reaction conditions in different atmospheric environments ranging from unpolluted to highly polluted.

  2. (4 + 3) Cycloadditions of Nitrogen-Stabilized Oxyallyl Cations

    Science.gov (United States)

    Lohse, Andrew G.; Hsung, Richard P.

    2011-01-01

    The use of heteroatom-substituted oxyallyl cations in (4 + 3) cycloadditions has had a tremendous impact on the development of cycloaddition chemistry. Extensive efforts have been exerted toward investigating the effect of oxygen-, sulfur-, and halogen-substituents on the reactivity of oxyallyl cations. Most recently, the use of nitrogen-stabilized oxyallyl cations has gained prominence in the area of (4 + 3) cycloadditions. The following article will provide an overview of this concept utilizing nitrogen-stabilized oxyallyl cations. PMID:21384451

  3. Cation-Cation Complexes of Pentavalent Uranyl: From Disproportionation Intermediates to Stable Clusters

    Energy Technology Data Exchange (ETDEWEB)

    Mougel, Victor; Horeglad, Pawel; Nocton, Gregory; Pecaut, Jacques; Mazzanti, Marinella [CEA, INAC, SCIB, Laboratoire de Reconnaissance Ionique et Chimie de Coordination, CEA-Grenoble, 38054 GRENOBLE, Cedex 09 (France)

    2010-07-01

    Three new cation cation complexes of pentavalent uranyl, stable with respect to the disproportionation reaction, have been prepared from the reaction of the precursor [(UO{sub 2}py{sub 5})-(KI{sub 2}py{sub 2})]{sub n} (1) with the Schiff base ligands salen{sup 2-}, acacen{sup 2-}, and salophen{sup 2-} (H{sub 2}salen N, N'-ethylene-bis(salicylidene-imine), H{sub 2}acacen=-N, N'-ethylenebis(acetylacetone-imine), H{sub 2}salophen=N, N'-phenylene-bis(salicylidene-imine)). The preparation of stable complexes requires a careful choice of counter ions and reaction conditions. Notably the reaction of 1 with salophen{sup 2-} in pyridine leads to immediate disproportionation, but in the presence of [18]crown-6 ([18]C-6) a stable complex forms. The solid-state structure of the four tetra-nuclear complexes ([UO{sub 2}-(acacen)]{sub 4}[{mu}{sub 8}-]{sub 2}[K([18]C-6)(py)]{sub 2}) (3) and ([UO{sub 2}(acacen)](4)[{mu}{sub 8}-]).2[K([222])(py)] (4) ([UO{sub 2}(salophen)](4)[{mu}{sub 8}-K]{sub 2}[mu(5)-KI]{sub 2}[(K([18]C-6)]).2 [K([18]C-6)-(thf){sub 2}].2I (5), and ([UO{sub 2}(salen)(4)][{mu}{sub 8}-Rb]{sub 2}[Rb([18]C-6)]{sub 2}) (9) ([222] = [222]cryptand, py =pyridine), presenting a T-shaped cation cation interaction has been determined by X-ray crystallographic studies. NMR spectroscopic and UV/Vis studies show that the tetra-nuclear structure is maintained in pyridine solution for the salen and acacen complexes. Stable mononuclear complexes of pentavalent uranyl are also obtained by reduction of the hexavalent uranyl Schiff base complexes with cobaltocene in pyridine in the absence of coordinating cations. The reactivity of the complex [U{sup V}O{sub 2}(salen)(py)][Cp*{sub 2}Co] with different alkali ions demonstrates the crucial effect of coordinating cations on the stability of cation cation complexes. The nature of the cation plays a key role in the preparation of stable cation cation complexes. Stable tetra-nuclear complexes form in the presence of K

  4. Thermochemical stability of Soviet macroporous sulfonated cation-exchangers

    Energy Technology Data Exchange (ETDEWEB)

    Rukhlyada, N.N.; Plotnikova, V.P.; Roginskaya, B.S.; Znamenskii, Yu.P.; Zavodovskaya, A.S.; Dobrova, E.I.

    1988-10-20

    The purpose of this work was to study the influence of macroporosity on the thermochemical stability of sulfonated cation-exchangers. The investigations were carried out on commercial macroporous sulfonated cation-exchangers based on styrene-divinylbenzene copolymers. Study of the thermochemical stability of macroporous sulfonated cation-exchangers in dilute hydrogen peroxide solutions showed that the type of macroporosity has virtually no influence on their stability. The determining factor in thermal stability of macroporous cation-exchangers, as of the gel type, is the degree of cross-linking of the polymer matrix. The capacity loss of macroporous cation-exchangers during oxidative thermolysis is caused by destruction of the macromolecular skeleton and elution of fragments of polar chains containing sulfo groups into the solution.

  5. Stability and recovery of DNA origami structure with cation concentration

    Science.gov (United States)

    Chen, Yi; Wang, Ping; Liu, Yang; Liu, Ting; Xu, Yan; Zhu, Shanshan; Zhu, Jun; Ye, Kai; Huang, Guang; Dannong, He

    2018-01-01

    We synthesized triangular and rectangular DNA origami nanostructures and investigated the stability and recovery of them under low cation concentration. Our results demonstrated that the origami nanostructures would melt when incubated in low cation concentration, and recover whilst kept in the concentration for less than 10 min. However, extending the incubation time would lead to irreversible melting. Our results show the possibility of application of DNA origami nanostructures for things such as a sensor for cation concentration response, etc.

  6. Stability of anionic polymers in presence of multivalent cations

    International Nuclear Information System (INIS)

    Sabbagh, Imad

    1997-01-01

    The objectives of this research thesis were to study the stability of poly-electrolytes in saline environments, and the interactions between ions and poly-electrolytes of different charge densities. After a recall of the properties of neutral polymers and of poly-electrolytes in solution, the author evokes the interactions between poly-electrolytes and counter-ions, and briefly presents two models of stability of poly-electrolytes in saline solutions. Then, he presents different experimental techniques (scattering techniques and electrochemical techniques) and the results obtained when characterizing the used compounds. In the next part, the author discusses the basic differences of solubility between poly-electrolytes with sulfonate or sulfate groups and those with carboxylate groups. A simple model, inspired by the electrostatic model, allows poly-electrolyte phase diagram to be generalised with respect to the chemical affinity of its functional group with ions of opposed sign. The author then reports the study of the behaviour of non-charged poly-acrylic acid in various saline solutions, and then checks the behaviour of this acid within an intermediate range of dissociation level. The poly-acrylic acid structure and the distribution of ions before de-mixing are studied by X-ray and neutron scattering. The author finally tries to understand what is going on when multivalent cations are replaced by positively charged nano-metric particles (dendrimers) [fr

  7. Formation, structure, and stability of MHD intermediate shocks

    International Nuclear Information System (INIS)

    Wu, C.C.

    1990-01-01

    Contrary to the usual belief that MHD intermediate shocks are extraneous, the author has recently shown by numerical solutions of dissipative MHD equations that intermediate shocks are admissible and can be formed through nonlinear wave steepening from continuous waves. In this paper, the formation, structure and stability of intermediate shocks in dissipative MHD are considered in detail. The differences between the conventional theory and his are pointed out and clarified. He shows that all four types of intermediate shocks can be formed from smooth waves. He also shows that there are free parameters in the structure of the intermediate shocks, and that these parameters are related to the shock stability. In addition, he shows that a rotational discontinuity can not exist with finite width, indicate how this is related to the existence of time-dependent intermediate shocks, and show why the conventional theory is not a good approximation to dissipative MHD solutions whenever there is rotation in magnetic field

  8. On the stability of rotational discontinuities and intermediate shocks

    International Nuclear Information System (INIS)

    Lee, L.C.; Huang, L.; Chao, J.K.

    1989-01-01

    The stability of rotational discontinuities and intermediate shocks is studied based on a hybrid simulation code. The simulation results show that rotational discontinuities are stable and intermediate shocks are not stationary. Intermediate shocks tend to evolve to rotational discontinuities and waves. The authors employ several different initial profiles for the magnetic field in the transition region and find that the final structure of the discontinuities or shocks is not sensitive to the initial magnetic field profile. The present results are different from those obtained from the resistive MHD simulations. Furthermore, their study indicates that the kinetic effect of particles plays an important role in the structure and stability of rotational discontinuities and intermediate shocks

  9. Incorporating Graphene Oxide into Alginate Polymer with a Cationic Intermediate To Strengthen Membrane Dehydration Performance.

    Science.gov (United States)

    Guan, Kecheng; Liang, Feng; Zhu, Haipeng; Zhao, Jing; Jin, Wanqin

    2018-04-25

    Two-dimensional graphene oxide (GO) in hybrid membranes provides fast water transfer across its surface due to the abundant oxygenated functional groups to afford water sorption and the hydrophobic basal plane to create fast transporting pathways. To establish more compatible and efficient interactions for GO and sodium alginate (SA) polymer chains, cations sourced from lignin are employed to decorate GO (labeled as cation-functionalized GO (CG)) nanosheets via cation-π and π-π interactions, providing more interactive sites to confer synergetic benefits with polymer matrix. Cations from CG are also functional to partially interlock SA chains and intensify water diffusion. And with the aid of two-dimensional pathways of CG, fast selective water permeation can be realized through hybrid membranes with CG fillers. In dehydrating aqueous ethanol solution, the hybrid membrane exhibits considerable performance compared with bare SA polymer membrane (long-term stable permeation flux larger than 2500 g m -2 h -1 and water content larger than 99.7 wt %, with feed water content of 10 wt % under 70 °C). The effects of CG content in SA membrane were investigated, and the transport mechanism was correspondingly studied through varying operation conditions and membrane materials. In addition, such a membrane possesses long-term stability and almost unchanged high dehydration capability.

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

    International Nuclear Information System (INIS)

    Tahara, S.; Kawakita, Y.; Shimakura, H.; Ohara, K.; Fukami, T.; Takeda, S.

    2015-01-01

    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 AgAg (Q) and S RbRb (Q), show a positive contribution to the FSDP, while S 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

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

    Energy Technology Data Exchange (ETDEWEB)

    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)

    2015-07-28

    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.

  12. Stability of anionic polymers in presence of multivalent cations

    International Nuclear Information System (INIS)

    Sabbagh, Imad

    1997-01-01

    This research thesis aimed at studying the stability of poly-electrolytes in saline environments, and the interactions between ions and poly-electrolytes of different charge densities. For this purpose, the author more particularly studied specific interactions between anionic poly-electrolytes and multivalent cations. After a recall of properties of neutral polymers and poly-electrolytes in solution, the author evokes interactions between poly-electrolytes and counter-ions, and briefly presents two models of stability of poly-electrolytes in saline solutions. The next part presents various experimental spectroscopic and electrochemical techniques and results of the characterization of the used products. Spectroscopic techniques allow ion-polymer interactions at the atomic scale to be studied, and electrochemical techniques allow the behaviour of small ions to be studied. The author then discusses the main differences of solubility between poly-electrolytes containing sulphonate or sulphate groups and those containing carboxylate groups. A model is then developed to generalise phase diagrams of a poly-electrolyte with respect to the chemical affinity of its functional group with ions of opposite sign. The author then addresses the behaviour of a non charged polyacrylic acid in various saline solutions, and presents a phase diagram model [fr

  13. Storage Stability and Improvement of Intermediate Moisture Foods, Phase 3

    Science.gov (United States)

    Labuza, T. P.

    1975-01-01

    Methods were determined for the improvement of shelf-life stability of intermediate moisture foods (IMF). Microbial challenge studies showed that protection against molds and Staphylococcus aureus could be achieved by a combination of antimicrobial agents, humectants and food acids. Potassium sorbate and propylene glycol gave the best results. It was also confirmed that the maximum in heat resistance shown by vegetative pathogens at intermediate water activities also occurred in a solid food. Glycols and sorbitol both achieve browning inhibition because of their action as a medium for reaction and effect on viscosity of the adsorbed phase. Chemical availability results showed rapid lysine loss before visual discoloration occurred. This is being confirmed with a biological test using Tetrahymena pyriformis W. Accelerated temperature tests show that effectiveness of food antioxidants against rancidity development can be predicted; however, the protection factor changes with temperature. BHA was found to be the best antioxidant for iron catalyzed oxidation.

  14. Thermal stability of intermediate band behavior in Ti implanted Si

    Energy Technology Data Exchange (ETDEWEB)

    Olea, J.; Pastor, D.; Martil, I.; Gonzalez-Diaz, G. [Dpto. De Fisica Aplicada III (Electricidad y Electronica), Facultad de Ciencias Fisicas, Universidad Complutense de Madrid, E-28040 Madrid (Spain)

    2010-11-15

    Ti implantation in Si with very high doses has been performed. Subsequent Pulsed Laser Melting (PLM) annealing produces good crystalline lattice with electrical transport properties that are well explained by the Intermediate Band (IB) theory. Thermal stability of this new material is analyzed by means of isochronal annealing in thermodynamic equilibrium conditions at increasing temperature. A progressive deactivation of the IB behavior is shown during thermal annealing, and structural and electrical measurements are reported in order to find out the origin of this result. (author)

  15. Stabilizing intermediate-term medium-range earthquake predictions

    International Nuclear Information System (INIS)

    Kossobokov, V.G.; Romashkova, L.L.; Panza, G.F.; Peresan, A.

    2001-12-01

    A new scheme for the application of the intermediate-term medium-range earthquake prediction algorithm M8 is proposed. The scheme accounts for the natural distribution of seismic activity, eliminates the subjectivity in the positioning of the areas of investigation and provides additional stability of the predictions with respect to the original variant. According to the retroactive testing in Italy and adjacent regions, this improvement is achieved without any significant change of the alarm volume in comparison with the results published so far. (author)

  16. Role of specific cations and water entropy on the stability of branched DNA motif structures.

    Science.gov (United States)

    Pascal, Tod A; Goddard, William A; Maiti, Prabal K; Vaidehi, Nagarajan

    2012-10-11

    DNA three-way junctions (TWJs) are important intermediates in various cellular processes and are the simplest of a family of branched nucleic acids being considered as scaffolds for biomolecular nanotechnology. Branched nucleic acids are stabilized by divalent cations such as Mg(2+), presumably due to condensation and neutralization of the negatively charged DNA backbone. However, electrostatic screening effects point to more complex solvation dynamics and a large role of interfacial waters in thermodynamic stability. Here, we report extensive computer simulations in explicit water and salt on a model TWJ and use free energy calculations to quantify the role of ionic character and strength on stability. We find that enthalpic stabilization of the first and second hydration shells by Mg(2+) accounts for 1/3 and all of the free energy gain in 50% and pure MgCl(2) solutions, respectively. The more distorted DNA molecule is actually destabilized in pure MgCl(2) compared to pure NaCl. Notably, the first shell, interfacial waters have very low translational and rotational entropy (i.e., mobility) compared to the bulk, an entropic loss that is overcompensated by increased enthalpy from additional electrostatic interactions with Mg(2+). In contrast, the second hydration shell has anomalously high entropy as it is trapped between an immobile and bulklike layer. The nonmonotonic entropic signature and long-range perturbations of the hydration shells to Mg(2+) may have implications in the molecular recognition of these motifs. For example, we find that low salt stabilizes the parallel configuration of the three-way junction, whereas at normal salt we find antiparallel configurations deduced from the NMR. We use the 2PT analysis to follow the thermodynamics of this transition and find that the free energy barrier is dominated by entropic effects that result from the decreased surface area of the antiparallel form which has a smaller number of low entropy waters in the first

  17. Synthesis, Structure and Reactivity of a Borylene Cation [(NHSi)2B(CO)]+ Stabilized by Three Neutral Ligands.

    Science.gov (United States)

    Wang, Hao; Wu, Linlin; Lin, Zhenyang; Xie, Zuowei

    2017-10-04

    A borylene cation stabilized by bis(silylene) and carbon monoxide was prepared and structurally characterized via the reaction of bis(silylene)-stabilized bromoborylene with W(CO) 6 . This is the first example of a borylene cation coordinated by three neutral ligands, which can be viewed as a cationic form of a long-sought Lewis base-stabilized zerovalent boron compound. This cation can cleave dihydrogen.

  18. Stabilization of sulfide cations: mechanisms relevant to oxidation of peptides and proteins containing methionine

    International Nuclear Information System (INIS)

    Bobrowski, K.; Hug, G.L.; Pogocki, D.; Horner, G.; Marciniak, B.; Schoneich, C.

    2006-01-01

    Sulfide radical cations (R 2 S +. ) have recently attracted considerable attention. In particular they are implicated in assorted biological electron transfers where they are likely intermediates in biological redox-processes. There is unambigous theoretical and experimental evidence that R 2 S +. can be stabilized through intramolecular complexation with nucleophiles that are present in neighboring groups. Reactions of this type are of special interest to biology when stabilization of sulfide radical cations derived from methionine, Met(>S +. ) occurs in peptides and proteins. The methionine (Met) residues in these biopolymers are susceptible to attack by Reactive Oxygen Species (ROS) during oxidative stress and biological aging. Moreover, the pathogenesis of some neurodegenerative diseases (Alzheimer's, Jacob-Creutzfeld's, and Parkinson's) seems to be strongly linked to the presence in brain tissue of β-amyloid peptide (βAP), human prion protein (hPrP), and an aggregated form of α-synuclein, respectively. These macro- molecules contain methionine(s) with βAP having a Met 35 residue in its C-terminal α-helical domain, hPrP having three out of nine Met-residues (namely Met 205 , Met 206 , and Met 213 ) located within its α-helical segments, and α-synuclein having four Met-residues. The effective neighboring-group interactions would likely involve nucleophilic functionalities in the side chain of amino acids residues. However, very often heteroatoms in peptide bonds are the only nucleophiles present in the vicinity of Met(>S +. ). In this regard, it was recently shown that such interactions play an important role in N-acetylmethione amide and in oligopeptides of the form N-Ac-Gly-Met-Gly and N-Ac-Gly-(Gly) 2 -Met-(Gly) 3 . Intramolecularly bonded sulfide radical cations, Met(>S +. ), were directly observed in these systems with the bonding partner being either the carbonyl oxygen or the amide nitrogen of a peptide bond. Cyclic dipeptides are suitable model

  19. Contribution of cation-π interactions to the stability of Sm/LSm oligomeric assemblies.

    Science.gov (United States)

    Mucić, Ivana D; Nikolić, Milan R; Stojanović, Srđan Đ

    2015-07-01

    In this work, we have analyzed the influence of cation-π interactions to the stability of Sm/LSm assemblies and their environmental preferences. The number of interactions formed by arginine is higher than lysine in the cationic group, while histidine is comparatively higher than phenylalanine and tyrosine in the π group. Arg-Tyr interactions are predominant among the various pairs analyzed. The furcation level of multiple cation-π interactions is much higher than that of single cation-π interactions in Sm/LSm interfaces. We have found hot spot residues forming cation-π interactions, and hot spot composition is similar for all aromatic residues. The Arg-Phe pair has the strongest interaction energy of -8.81 kcal mol(-1) among all the possible pairs of amino acids. The extent of burial of the residue side-chain correlates with the ΔΔG of binding for residues in the core and also for hot spot residues cation-π bonded across the interface. Secondary structure of the cation-π residues shows that Arg and Lys preferred to be in strand. Among the π residues, His prefers to be in helix, Phe prefers to be in turn, and Tyr prefers to be in strand. Stabilization centers for these proteins showed that all the five residues found in cation-π interactions are important in locating one or more of such centers. More than 50 % of the cation-π interacting residues are highly conserved. It is likely that the cation-π interactions contribute significantly to the overall stability of Sm/LSm proteins.

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

    Directory of Open Access Journals (Sweden)

    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.

  1. Quantitative Characterization of Non-Classic Polarization of Cations on Clay Aggregate Stability

    Science.gov (United States)

    Hu, Feinan; Li, Hang; Liu, Xinmin; Li, Song; Ding, Wuquan; Xu, Chenyang; Li, Yue; Zhu, Longhui

    2015-01-01

    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. PMID:25874864

  2. Delocalization does not always stabilize : a quantum chemical analysis of -substituent effects on 54 alkyl and vinyl cations

    NARCIS (Netherlands)

    Alem, van K.; Lodder, G.; Zuilhof, H.

    2002-01-01

    The effects of -substituents on alkyl and vinyl cations are studied using high-level ab initio calculations. The geometries, stabilities, and electronic properties of 27 alkyl cations and 27 vinyl cations with -substituents are computed at the B3LYP/6-311 G(d,p), MP2/6-311 G(d,p), and CBS-Q levels.

  3. Kinetic Monte Carlo Simulation of Oxygen and Cation Diffusion in Yttria-Stabilized Zirconia

    Science.gov (United States)

    Good, Brian

    2011-01-01

    Yttria-stabilized zirconia (YSZ) is of interest to the aerospace community, notably for its application as a thermal barrier coating for turbine engine components. In such an application, diffusion of both oxygen ions and cations is of concern. Oxygen diffusion can lead to deterioration of a coated part, and often necessitates an environmental barrier coating. Cation diffusion in YSZ is much slower than oxygen diffusion. However, such diffusion is a mechanism by which creep takes place, potentially affecting the mechanical integrity and phase stability of the coating. In other applications, the high oxygen diffusivity of YSZ is useful, and makes the material of interest for use as a solid-state electrolyte in fuel cells. The kinetic Monte Carlo (kMC) method offers a number of advantages compared with the more widely known molecular dynamics simulation method. In particular, kMC is much more efficient for the study of processes, such as diffusion, that involve infrequent events. We describe the results of kinetic Monte Carlo computer simulations of oxygen and cation diffusion in YSZ. Using diffusive energy barriers from ab initio calculations and from the literature, we present results on the temperature dependence of oxygen and cation diffusivity, and on the dependence of the diffusivities on yttria concentration and oxygen sublattice vacancy concentration. We also present results of the effect on diffusivity of oxygen vacancies in the vicinity of the barrier cations that determine the oxygen diffusion energy barriers.

  4. Divalent cations in tears, and their influence on tear film stability in humans and rabbits.

    Science.gov (United States)

    Wei, Xiaojia Eric; Markoulli, Maria; Millar, Thomas J; Willcox, Mark D P; Zhao, Zhenjun

    2012-06-05

    Reduced tear film stability is reported to contribute to dry eye. Rabbits are known to have a more stable tear film than humans. Thus, we sought to examine the tears of rabbits and humans for metal cations, and to test how they influence tear film stability. Tears were collected from 10 healthy humans and 6 rabbits. Tear osmolality was measured by vapor pressure osmometer, and metals analyzed using inductively coupled plasma (ICP) mass spectrometry or ICP atomic emission spectroscopy. The influence of divalent cations on tears was analyzed by measuring surface tension using the Langmuir trough in vitro, using different concentrations of cations in the subphase, and grading the tear break-up in rabbits in vivo after instillation of chelating agents. Rabbit tears had a higher osmolality compared to humans. Major metals did not differ between species; however, rabbits had higher levels of Mg(2+) (1.13 vs. 0.39 mM) and Ca(2+) (0.75 vs. 0.36 mM). In rabbit tears in vitro, diminishing divalent cations resulted in a decrease in the maximum surface pressure from 37 to 30 mN/m. In vivo, an increase in the amount of tear film that was broken-up was found. In contrast, when changing divalent cation concentrations in human tears, the maximum surface pressure remained at 26 mN/m. The normal osmolality of rabbit tears is significantly higher than that in humans. While divalent cations had little influence on human tears, they appear to have an important role in maintaining tear film stability in rabbits.

  5. Cation-Induced Stabilization and Denaturation of DNA Origami Nanostructures in Urea and Guanidinium Chloride.

    Science.gov (United States)

    Ramakrishnan, Saminathan; Krainer, Georg; Grundmeier, Guido; Schlierf, Michael; Keller, Adrian

    2017-11-01

    The stability of DNA origami nanostructures under various environmental conditions constitutes an important issue in numerous applications, including drug delivery, molecular sensing, and single-molecule biophysics. Here, the effect of Na + and Mg 2+ concentrations on DNA origami stability is investigated in the presence of urea and guanidinium chloride (GdmCl), two strong denaturants commonly employed in protein folding studies. While increasing concentrations of both cations stabilize the DNA origami nanostructures against urea denaturation, they are found to promote DNA origami denaturation by GdmCl. These inverse behaviors are rationalized by a salting-out of Gdm + to the hydrophobic DNA base stack. The effect of cation-induced DNA origami denaturation by GdmCl deserves consideration in the design of single-molecule studies and may potentially be exploited in future applications such as selective denaturation for purification purposes. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Effect of Cation Ordering on the Performance and Chemical Stability of Layered Double Perovskite Cathodes

    Directory of Open Access Journals (Sweden)

    Carlos Bernuy-Lopez

    2018-01-01

    Full Text Available The effect of A-site cation ordering on the cathode performance and chemical stability of A-site cation ordered LaBaCo2O5+δ and disordered La0.5Ba0.5CoO3−δ materials are reported. Symmetric half-cells with a proton-conducting BaZr0.9Y0.1O3−δ electrolyte were prepared by ceramic processing, and good chemical compatibility of the materials was demonstrated. Both A-site ordered LaBaCo2O5+δ and A-site disordered La0.5Ba0.5CoO3−δ yield excellent cathode performance with Area Specific Resistances as low as 7.4 and 11.5 Ω·cm2 at 400 °C and 0.16 and 0.32 Ω·cm2 at 600 °C in 3% humidified synthetic air respectively. The oxygen vacancy concentration, electrical conductivity, basicity of cations and crystal structure were evaluated to rationalize the electrochemical performance of the two materials. The combination of high-basicity elements and high electrical conductivity as well as sufficient oxygen vacancy concentration explains the excellent performance of both LaBaCo2O5+δ and La0.5Ba0.5CoO3−δ materials at high temperatures. At lower temperatures, oxygen-deficiency in both materials is greatly reduced, leading to decreased performance despite the high basicity and electrical conductivity. A-site cation ordering leads to a higher oxygen vacancy concentration, which explains the better performance of LaBaCo2O5+δ. Finally, the more pronounced oxygen deficiency of the cation ordered polymorph and the lower chemical stability at reducing conditions were confirmed by coulometric titration.

  7. Monovalent cation induced structural transitions in telomeric DNAs: G-DNA folding intermediates

    International Nuclear Information System (INIS)

    Hardin, C.C.; Watson, T.; Henderson, E.; Prosser, J.K.

    1991-01-01

    Telomeric DNA consists of G- and C-rich strands that are always polarized such that the G-rich strand extends past the 3' end of the duplex to form a 12-16-base overhang. These overhanging strands can self-associate in vitro to form intramolecular structures that have several unusual physical properties and at least one common feature, the presence of non-Watson-Crick G·G base pairs. The term G-DNA was coined for this class of structures. On the basis of gel electrophoresis, imino proton NMR, and circular dichroism (CD) results, the authors find that changing the counterions from sodium to potassium specifically induces conformational transitions in the G-rich telomeric DNA from Tetrahymena, d(T 2 G 4 ) 4 (TET4), which results in a change from the intramolecular species to an apparent multistranded structure, accompanied by an increase in the melting temperature of the base pairs of >25 degree, as monitored by loss of the imino proton NMR signals. They infer that the multistranded structure is a quadruplex. The results indicate that specific differences in ionic interactions can result in a switch in telomeric DNAs between intramolecular hairpin-like or quadruplex-containing species and intermolecular quadruplex structures, all of which involve G·G base pairing interaction. They propose a model in which duplex or hairpin forms of G-DNA are folding intermediates in the formation of either 1-, 2-, or 4-stranded quadruplex structures

  8. Role of the metal oxidation state in the SNS-Cr catalyst for ethylene trimerization: Isolation of Di- and trivalent cationic intermediates

    NARCIS (Netherlands)

    Jabri, A.; Temple, C.N.; Crewdson, P.; Gambarotta, S.; Korobkov, I.V.; Duchateau, R.

    2006-01-01

    The reaction of the highly selective [CySCH2CH2N(H)CH2CH2SCy]CrCl3 catalyst precursor with alkyl aluminum activators was examined with the aim of isolating reactive intermediates. Reaction with Me3Al afforded a cationic trivalent chromium alkyl species

  9. 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

    2012-01-01

    Diamine-cross-linked membranes were prepared from cross-linkable poly(arylene ether ketone) containing pendant cationic quaternary ammonium group (QPAEK) solution by a facile and general thermal curing method using 4,4′-diaminodiphenylmethane with rigid framework and 1,6-diaminohexane with flexible...... 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...... successfully operated at temperatures up to 120 °C and 180 °C with unhumidified hydrogen and air under ambient pressure, the maximum performance of diamine-cross-linked membrane is observed at 180 °C with a current density of 1.06 A cm−2 and the peak power density of 323 mW cm−2. The results also indicate...

  10. 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.

    2010-01-01

    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

  11. 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.

    2010-01-01

    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

  12. Alkyl ammonium cation stabilized biocidal polyiodides with adaptable high density and low pressure.

    Science.gov (United States)

    He, Chunlin; Parrish, Damon A; Shreeve, Jean'ne M

    2014-05-26

    The effective application of biocidal species requires building the active moiety into a molecular back bone that can be delivered and decomposed on demand under conditions of low pressure and prolonged high-temperature detonation. The goal is to destroy storage facilities and their contents while utilizing the biocidal products arising from the released energy to destroy any remaining harmful airborne agents. Decomposition of carefully selected iodine-rich compounds can produce large amounts of the very active biocides, hydroiodic acid (HI) and iodine (I2). Polyiodide anions, namely, I3(-), I5(-), which are excellent sources of such biocides, can be stabilized through interactions with large, symmetric cations, such as alkyl ammonium salts. We have designed and synthesized suitable compounds of adaptable high density up to 3.33 g cm(-3) that are low-pressure polyiodides with various alkyl ammonium cations, deliverable iodine contents of which range between 58.0-90.9%. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Thermodynamic stability and retinol binding property of {beta}-lactoglobulin in the presence of cationic surfactants

    Energy Technology Data Exchange (ETDEWEB)

    Sahihi, M. [Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111 (Iran, Islamic Republic of); Bordbar, A.K., E-mail: bordbar@chem.ui.ac.ir [Department of Chemistry, University of Isfahan, Isfahan 81746-73441 (Iran, Islamic Republic of); Ghayeb, Y. [Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111 (Iran, Islamic Republic of)

    2011-08-15

    Highlights: > The stability parameters of {beta}-lactoglobulin, BLG, in the presence of C{sub n}TAB have been evaluated. > Rising in hydrocarbon chain length increases the denaturating power of surfactants. > C{sub n}TAB enhances the retinol binding affinity of BLG in all of its concentration range. - Abstract: In this work the stability parameters of bovine {beta}-lactoglobulin, variant A (BLG-A), with regard to their transition curves induced by dodecyltrimethylammonium bromide (C{sub 12}TAB), tetradecyltrimethylammonium bromide (C{sub 14}TAB) and hexadecyltrimethylammonium bromide (C{sub 16}TAB) as cationic surfactants, were determined at 298 K. For each transition curve, the conventional method of analysis which assumes a linear concentration dependence of the pre- and post-transition base lines, gave the most realistic values for {Delta}G{sub D}(H{sub 2}O). The results represent the increase in the denaturating power of surfactants with an increase in hydrocarbon chain length. The value of about 22.27 kJ . mol{sup -1} was obtained for {Delta}G{sub D}(H{sub 2}O) from transition curves. Subsequently, the retinol binding property of BLG as its functional indicator was investigated in the presence of these surfactants using the spectrofluorimeter titration method. The results represent the substantial enhancement of retinol binding affinity of BLG in the presence of these surfactants.

  14. Stabilization of cationic and anionic metal species in contaminated soils using sludge-derived biochar.

    Science.gov (United States)

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

    2016-04-01

    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. Copyright © 2016 Elsevier Ltd. All rights reserved.

  15. Stability and isomerization reactions of phenyl cation C{sub 6}H{sub 5}{sup +} isomers

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Dandan [Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012 (China); Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun 130012 (China); Yang, Xue [College of Science, Jilin Institute of Chemical Technology, Jilin 132022 (China); Zhang, Xiaomei; Shan, Shimin [Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012 (China); Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun 130012 (China); Xu, Haifeng, E-mail: xuhf@jlu.edu.cn [Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012 (China); Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun 130012 (China); Yan, Bing, E-mail: yanbing@jlu.edu.cn [Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012 (China); Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun 130012 (China)

    2016-03-01

    Highlights: • A total of 60 isomers of C{sub 6}H{sub 5}{sup +} cations were obtained at density functional theory. • The stability and isomerization reactions of C{sub 6}H{sub 5}{sup +} isomers were performed. • The structures, frequencies, thermodynamic properties of isomers were summarized. • Ring to ring or chain isomerization pathways were investigated using IRC method. • Result shows reactions contain hydrogen transfer, bond broken and reconstruction. - Abstract: As a key polyatomic molecular cation that plays a pivotal role in growth of the polycyclic aromatic hydrocarbons, phenyl cation C{sub 6}H{sub 5}{sup +} exhibits various isomers and isomerization reactions. Investigation on the structure and stability of the isomers as well as the isomerization is important for better understanding the chemical reactions involving C{sub 6}H{sub 5}{sup +} cations. In this work, we have performed a theoretical study on the stability and isomerization reactions of C{sub 6}H{sub 5}{sup +} isomers at density functional theory B3LYP/6-311G (d, p) level. We have obtained a total of 60 isomers of C{sub 6}H{sub 5}{sup +} cations, most of which are reported for the first time. The geometries, vibrational frequencies, thermodynamic properties and stability of 28 out of 60 isomers have been summarized in detail. Different ring-to-ring and ring-to-chain isomerization pathways, which are connected via 28 transition states, have been investigated using the intrinsic reaction coordinate method. The results show that the isomerization reactions occur via hydrogen migration followed by bond-breaking and reconstruction.

  16. Nanocapsule of cationic liposomes obtained using "in situ" acrylic acid polymerization: stability, surface charge and biocompatibility.

    Science.gov (United States)

    Scarioti, Giovana Danieli; Lubambo, Adriana; Feitosa, Judith P A; Sierakowski, Maria Rita; Bresolin, Tania M B; de Freitas, Rilton Alves

    2011-10-15

    In this work, didecyldimethylammonium bromide (DDAB) and 1,2-dioleoyl-sn-glycero-3-phosphatidylethanolamine (DOPE) (2.5:1) were used to prepare liposomes coated with polyacrylic acid (PAA) using "in situ" polymerization with 2.5, 5 and 25 mM of acrylic acid (AA). The PAA concentrations were chosen to achieve partially to fully covered capsules, and the polymerization reaction was observed with real-time monitoring using dynamic light scattering (NanoDLS). The DDAB:DOPE liposomes showed stability in the tested temperature range (25-70°C), whereas the results confirmed the success of the polymerization according to superficial charge (zeta potential of +66.7±1.2 mV) results and AFM images. For the liposomes that were fully coated with PAA (zeta potential of +0.3±3.9 mV), cytotoxicity was independent of the concentration of albumin. Cationic liposomes and nanocapsules of the stable liposomes coated with PAA were obtained by controlling the surface charge, which was the most important factor related to cytotoxicity. Thus, a potential, safe drug nanocarrier was successfully developed in this work. Copyright © 2011 Elsevier B.V. All rights reserved.

  17. Impact assessment of intermediate soil cover on landfill stabilization by characterizing landfilled municipal solid waste.

    Science.gov (United States)

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

    2013-10-15

    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. Copyright © 2013 Elsevier Ltd. All rights reserved.

  18. 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.

    Science.gov (United States)

    Tsuzuki, Seiji; Kubota, Keigo; Matsumoto, Hajime

    2013-12-19

    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

  19. Formation of an intermediate radical cation in the nanosecond pulse radiolysis of malachite green leucocyanide in organic solvents

    International Nuclear Information System (INIS)

    Grodkowski, J.; Bobrowski, K.; Mehnert, R.; Brede, O.

    1989-01-01

    The malachite green leucocyanide (MGCN) was irradiated in argon or oxygen saturated solutions of n-butyl chloride, 1.2-DCE, CCl 4 and acetone with 13 ns electron pulses. Two species with absorption maxima at 620 and 480 nm were observed. The latter was attributed to the malachite green leucocyanide radical cation (MGCN +radical ) and the former to the known carbonium ion of malachite green dye (MG + ). Observation of the consecutive charge transfer via the schemes: DCE +radical → BPh +radical → MGCN +radical and DCE +radical → MGCN +radical → TMPD +radical , allowed to estimate the ionization potential of MGCN molecule in the range 6.9 eV MGCN +radical radical cation is located in the ''aniline'' part of the molecule. (author)

  20. Formation of an intermediate radical cation in the nanosecond pulse radiolysis of malachite green leucocyanide in organic solvents

    Energy Technology Data Exchange (ETDEWEB)

    Grodkowski, J; Bobrowski, K; Mehnert, R; Brede, O

    1989-01-01

    The malachite green leucocyanide (MGCN) was irradiated in argon or oxygen saturated solutions of n-butyl chloride, 1.2-DCE, CCl/sub 4/ and acetone with 13 ns electron pulses. Two species with absorption maxima at 620 and 480 nm were observed. The latter was attributed to the malachite green leucocyanide radical cation (MGCN/sup +radical/) and the former to the known carbonium ion of malachite green dye (MG/sup +/). Observation of the consecutive charge transfer via the schemes: DCE/sup +radical/ -> BPh/sup +radical/ -> MGCN/sup +radical/ and DCE/sup +radical/ -> MGCN/sup +radical/ -> TMPD/sup +radical/, allowed to estimate the ionization potential of MGCN molecule in the range 6.9 eV < Ip/sub MGCN/ < 8.27 eV. Presented results and literature data suggest that positive charge in MGCN/sup +radical/ radical cation is located in the ''aniline'' part of the molecule. (author).

  1. Stability of Major Geogenic Cations in Drinking Water - An Issue of Public Health Importance

    DEFF Research Database (Denmark)

    Wodschow, Kirstine; Hansen, Birgitte; Schullehner, Jörg

    2018-01-01

    Concentrations and spatial variations of the four cations Na, K, Mg and Ca are known to some extent for groundwater and to a lesser extent for drinking water. Using Denmark as case, the purpose of this study was to analyze the spatial and temporal variations in the major cations in drinking water...

  2. Advances in heterocycle synthesis via [3+m]-cycloaddition reactions involving an azaoxyallyl cation as the key intermediate.

    Science.gov (United States)

    Xuan, Jun; Cao, Xia; Cheng, Xiao

    2018-05-17

    Heterocyclic compounds are widely found in many natural isolates and medicinally relevant compounds, as well as some fine chemicals. The development of general and efficient methods for the construction of heterocyclic compounds is one of the most important tasks in synthetic organic chemistry. Along these lines, [3+m]-cycloaddition reactions involving in situ generated azaoxyallyl cations as the 3-atom units have emerged as a powerful method for the synthesis of nitrogen-containing heterocycles. In this feature article, we highlight recent advances in this rapidly growing area, mainly focusing on the reaction design as well as the reaction mechanism.

  3. 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

    2016-06-01

    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.

  4. The thermodynamic stability of hydrogen bonded and cation bridged complexes of humic acid models-A theoretical study

    International Nuclear Information System (INIS)

    Aquino, Adelia J.A.; Tunega, Daniel; Pasalic, Hasan; Haberhauer, Georg; Gerzabek, Martin H.; Lischka, Hans

    2008-01-01

    Hydrogen bonded and cation bridged complexation of poly(acrylic acid) oligomers, representing a model compound for humic acids, with acetic acid and the herbicide (4-chloro-2-methylphenoxy) acetic acid (MCPA) have been studied by means of density functional theory. Solvation effects were computed by means of a combination of microsolvation (explicit insertion of water molecules) and global solvation (polarizable continuum approach). The stability of hydrogen bonded complexes in solution is characterized by a strong competition between solute and solvent molecules. The cation bridged complexes of the negatively charged (deprotonated) ligands were found to be strongly favored explaining the capability of humic acids to fixate anionic species from soil solutions and the ability to form cross-linking structures within the humic acid macromolecules

  5. The adenosine-triphosphatase system responsible for cation transport in electric organ: exclusion of phospholipids as intermediates

    Science.gov (United States)

    Glynn, I. M.; Slayman, Carolyn W.; Eichberg, J.; Dawson, R. M. C.

    1965-01-01

    1. Subcellular fractions were prepared from the electric organs of Electrophorus and Torpedo and assayed for adenosine-triphosphatase activity. 2. Treatment of the `low-speed' fraction from Torpedo with m-urea gave an adenosine-triphosphatase preparation that was almost completely (98%) inhibited by ouabain (0·1mg./ml.) and dependent on the simultaneous presence of Na+ and K+. 3. The adenosine-triphosphatase preparations were exposed to [γ-32P]ATP for 30sec. in the presence of (i) Na+, (ii) K+, (iii) Na++K+ and (iv) Na++K++ouabain. No significant labelling of phosphatidic acid, triphosphoinositide or any other phospholipid was observed. 4. The results suggest that phospholipids do not act as phosphorylated intermediates in the `transport adenosine-triphosphatase' system of electric organ. PMID:14340060

  6. Towards NHC stabilized alkylgallium alkoxide/aryloxide cations – The advances, the limitations and the challenges

    Czech Academy of Sciences Publication Activity Database

    Dabrowska, A. M.; Hurko, A.; Dranka, M.; Varga, Vojtěch; Urbańczyk, M.; Horegland, P.

    2017-01-01

    Roč. 840, JUL 2017 (2017), s. 63-69 ISSN 0022-328X R&D Projects: GA ČR(CZ) GA14-08531S Institutional support: RVO:61388955 Keywords : carbene * cations * gallium Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 2.184, year: 2016

  7. High-temperature stability of the hydrate shell of a Na+ cation in a flat nanopore with hydrophobic walls

    Science.gov (United States)

    Shevkunov, S. V.

    2017-11-01

    The effect of elevated temperature has on the hydrate shell of a singly charged sodium cation inside a flat nanopore with smooth walls is studied using the Monte Carlo method. The free energy and the entropy of vapor molecule attachment are calculated by means of a bicanonical statistical ensemble using a detailed model of interactions. The nanopore has a stabilizing effect on the hydrate shell with respect to fluctuations and a destabilizing effect with respect to complete evaporation. At the boiling point of water, behavior is observed that is qualitatively similar to behavior at room temperature, but with a substantial shift in the vapor pressure and shell size.

  8. The Free Tricoordinated Silyl Cation Problem

    Directory of Open Access Journals (Sweden)

    Čičak, H.

    2010-03-01

    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.

  9. Tuning the Relative Stability and Reactivity of Manganese Dioxygen and Peroxo Intermediates via Systematic Ligand Modification.

    Science.gov (United States)

    Kovacs, Julie A

    2015-10-20

    Many fundamental processes of life depend on the chemical energy stored in the O–O bond of dioxygen (O2), the majority of which is derived from photosynthetic H2O oxidation. Key steps in these processes involve Mn-, Fe-, or Cu-promoted formation or cleavage of O–O and O–H bonds, the mechanisms of which are not fully understood, especially with Mn. Metal–peroxo and high-valent metal–oxo species are proposed to be involved as intermediates. The metal ion properties that favor O–O and O–H bond formation versus cleavage have yet to be systematically explored. Herein we examine the O2 reactivity of a series of structurally related Mn(II) complexes and show that several metastable intermediates are observed, the relative stabilities of which depend on subtle differences in ligand architecture. We show that in contrast to Fe and Cu complexes, O2 binds irreversibly to Mn(II). By crystallizing an entire series of the first reported examples of Mn(III)–OOR peroxos as well as an O2-derived binuclear trans-μ-1,2-bridged Mn(III)–peroxo with varying degrees of O–O bond activation, we demonstrate that there are distinct correlations between spectroscopic, structural, and reactivity properties. Rate-limiting O–O bond cleavage is shown to afford a reactive species capable of abstracting H atoms from 2,4-tBu2-PhOH or 1,4-cyclohexadiene, depending on the ligand substituents. The weakly coordinated N-heterocycle Mn···Npy,quino distance is shown to correlate with the peroxo O–O bond length and modulate the π overlap between the filled πv*(O–O) and Mn dxz orbitals. We also show that there is a strong correlation between the peroxo → Mn charge transfer (CT) band and the peroxo O–O bond length. The energy difference between the CT bands associated with the peroxos possessing the shortest and longest O–O bonds shows that these distances are spectroscopically distinguishable. We show that we can use this spectroscopic parameter to estimate the O

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

    DEFF Research Database (Denmark)

    Gao, Tao; Norby, Poul

    2013-01-01

    precursor to the tunnel‐structured cryptomelane, in which the K+ ions play important roles in templating and stabilizing the tunneled framework. The presence of tunnel K+ ions also enhances the frame stability of the cryptomelane nanofibers at elevated temperatures. The formation of a layered KxMn2O4 (x ≈ 0...

  11. Light and Electrically Induced Phase Segregation and Its Impact on the Stability of Quadruple Cation High Bandgap Perovskite Solar Cells.

    Science.gov (United States)

    Duong, The; Mulmudi, Hemant Kumar; Wu, YiLiang; Fu, Xiao; Shen, Heping; Peng, Jun; Wu, Nandi; Nguyen, Hieu T; Macdonald, Daniel; Lockrey, Mark; White, Thomas P; Weber, Klaus; Catchpole, Kylie

    2017-08-16

    Perovskite material with a bandgap of 1.7-1.8 eV is highly desirable for the top cell in a tandem configuration with a lower bandgap bottom cell, such as a silicon cell. This can be achieved by alloying iodide and bromide anions, but light-induced phase-segregation phenomena are often observed in perovskite films of this kind, with implications for solar cell efficiency. Here, we investigate light-induced phase segregation inside quadruple-cation perovskite material in a complete cell structure and find that the magnitude of this phenomenon is dependent on the operating condition of the solar cell. Under short-circuit and even maximum power point conditions, phase segregation is found to be negligible compared to the magnitude of segregation under open-circuit conditions. In accordance with the finding, perovskite cells based on quadruple-cation perovskite with 1.73 eV bandgap retain 94% of the original efficiency after 12 h operation at the maximum power point, while the cell only retains 82% of the original efficiency after 12 h operation at the open-circuit condition. This result highlights the need to have standard methods including light/dark and bias condition for testing the stability of perovskite solar cells. Additionally, phase segregation is observed when the cell was forward biased at 1.2 V in the dark, which indicates that photoexcitation is not required to induce phase segregation.

  12. Efficient radical cation stabilization of PANI-ZnO and PANI-ZnO-GO composites and its optical activity

    Energy Technology Data Exchange (ETDEWEB)

    Mathavan, T., E-mail: tjmathavan@gmail.com; Divya, A.; Benial, A. Milton Franklin [PG & Research Department of Physics, N.M.S.S.Vellaichamy Nadar College, Madurai-625 019 (India); Archana, J. [Research Institute of Engineering, Shizuoka University (Japan); Ramasubbu, A. [PG & Research Department of Chemistry, Govt. Arts College, Coimbatore (India); Jothirajan, M. A. [Research Department of Physics, Arul Anandar College, Karumathur, Madurai-625 514 (India)

    2016-05-23

    Polyaniline (PANI) and its composites PANI-ZnO (Zinc oxide) and PANI-ZnO-GO (Graphene oxide) were successfully constructed. These materials were characterized by electron spin resonance (ESR) technique and ultraviolet visible spectrometry. The parameters such as line width, g-factor and spin concentration were deduced from ESR spectra, from the results the radical cation stabilization of PANI, PANI-ZnO and PANI-ZnO-GO composites were compared by the polaron and bipolaron formation. The absorption features obtained in the UV absorption spectra reveal the band gap of these modified PANI composites and also predicted the information of increasing and decreasing features of signal intensity and spin concentration.

  13. Efficient radical cation stabilization of PANI-ZnO and PANI-ZnO-GO composites and its optical activity

    International Nuclear Information System (INIS)

    Mathavan, T.; Divya, A.; Benial, A. Milton Franklin; Archana, J.; Ramasubbu, A.; Jothirajan, M. A.

    2016-01-01

    Polyaniline (PANI) and its composites PANI-ZnO (Zinc oxide) and PANI-ZnO-GO (Graphene oxide) were successfully constructed. These materials were characterized by electron spin resonance (ESR) technique and ultraviolet visible spectrometry. The parameters such as line width, g-factor and spin concentration were deduced from ESR spectra, from the results the radical cation stabilization of PANI, PANI-ZnO and PANI-ZnO-GO composites were compared by the polaron and bipolaron formation. The absorption features obtained in the UV absorption spectra reveal the band gap of these modified PANI composites and also predicted the information of increasing and decreasing features of signal intensity and spin concentration.

  14. Determination of stability constants of pyrophosphate complexes. 2. Influence of divalent cations: the magnesium

    International Nuclear Information System (INIS)

    Courriere, P.; Guillemart, A.; Besnard, J.-C.

    1978-01-01

    The stability constants of the complexes of pyrophosphate with magnesium have been determined directly from the titration curves of sodium pyrophosphate in presence of Mg 2+ with hydrochloric acid by a least-square iterative method at the temperature of 25 0 C and at a ionic strength adjusted to unity [fr

  15. Temperature effects on the stability of gold nanoparticles in the presence of a cationic thermoresponsive copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Pamies, Ramón [Technical University of Cartagena, Department of Material Engineering and Manufacturing (Spain); Zhu, Kaizheng [University of Oslo, Department of Chemistry (Norway); Kjøniksen, Anna-Lena, E-mail: anna.l.kjoniksen@hiof.no [Østfold University College, Faculty of Engineering (Norway); Nyström, Bo [University of Oslo, Department of Chemistry (Norway)

    2016-11-15

    New hybrid complexes composed by a thermoresponsive copolymer and gold nanoparticles (R{sub h} = 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.

  16. Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium.

    Science.gov (United States)

    Dau, Phuong D; Vasiliu, Monica; Peterson, Kirk A; Dixon, David A; Gibson, John K

    2017-12-06

    Actinyl chemistry is extended beyond Cm to BkO 2 + and CfO 2 + through transfer of an O atom from NO 2 to BkO + or CfO + , establishing a surprisingly high lower limit of 73 kcal mol -1 for the dissociation energies, D[O-(BkO + )] and D[O-(CfO + )]. CCSD(T) computations are in accord with the observed reactions, and characterize the newly observed dioxide ions as linear pentavalent actinyls; these being the first Bk and Cf species with oxidation states above IV. Computations of actinide dioxide cations AnO 2 + for An=Pa to Lr reveal an unexpected minimum for D[O-(CmO + )]. For CmO 2 + , and AnO 2 + beyond EsO 2 + , the most stable structure has side-on bonded η 2 -(O 2 ), as An III peroxides for An=Cm and Lr, and as An II superoxides for An=Fm, Md, and No. It is predicted that the most stable structure of EsO 2 + is linear [O=Es V =O] + , einsteinyl, and that FmO 2 + and MdO 2 + , like CmO 2 + , also have actinyl(V) structures as local energy minima. The results expand actinide oxidation state chemistry, the realm of the distinctive actinyl moiety, and the non-periodic character towards the end of the periodic table. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Comparing the short and long term stability of biodegradable, ceramic and cation exchange membranes in microbial fuel cells.

    Science.gov (United States)

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

    2013-11-01

    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. Copyright © 2013 Elsevier Ltd. All rights reserved.

  18. Cationic oligopeptides with the repeating sequence L-Lysyl-L-alanyl-L-alanine: conformational and thermal stability stuydy using optical spectroscopic methods

    Czech Academy of Sciences Publication Activity Database

    Setnička, V.; Hlaváček, Jan; Urbanová, J.

    2009-01-01

    Roč. 15, č. 8 (2009), s. 533-539 ISSN 1075-2617 Institutional research plan: CEZ:AV0Z40550506 Keywords : cationic peptides * conformation * thermal stability * vibrational circular dichroism Subject RIV: CC - Organic Chemistry Impact factor: 1.807, year: 2009

  19. The effect of positioning cations on acidity and stability of the framework structure of Y zeolite

    Science.gov (United States)

    Deng, Changshun; Zhang, Junji; Dong, Lihui; Huang, Meina; Bin Li; Jin, Guangzhou; Gao, Junbin; Zhang, Feiyue; Fan, Minguang; Zhang, Luoming; Gong, Yanjun

    2016-01-01

    The investigation on the modification of NaY zeolite on LaHY and AEHY (AE refers Ca and Sr and the molar ratio of Ca and Sr is 1:1) zeolites was proformed by XRD, N2-physisorption (BET), XRF, XPS, NH3-TPD, Py-IR, hydrothermal stability, and catalytic cracking test. These results indicate that HY zeolite with ultra low content Na can be obtained from NaY zeolite through four exchange four calcination method. The positioning capability of La3+ in sodalite cage is much better than that of AE2+ and about 12 La3+ can be well coordinated in sodalite cages of one unit cell of Y zeolite. Appropriate acid amount and strength favor the formation of propylene and La3+ is more suitable for the catalytic cracking of cyclohexane than that of AE2+. Our results not only elaborate the variation of the strong and weak acid sites as well as the Brönsted and Lewis acid sites with the change of exchanged ion content but also explore the influence of hydrothermal aging of LaHY and AEHY zeolites and find the optimum ion exchange content for the most reserved acid sites. At last, the coordination state and stabilization of ion exchanged Y zeolites were discussed in detail. PMID:26987306

  20. Synthesis of zirconia sol stabilized by trivalent cations (yttrium and neodymium or americium): a precursor for Am-bearing cubic stabilized zirconia.

    Science.gov (United States)

    Lemonnier, Stephane; Grandjean, Stephane; Robisson, Anne-Charlotte; Jolivet, Jean-Pierre

    2010-03-07

    Recent concepts for nuclear fuel and targets for transmuting long-lived radionuclides (minor actinides) and for the development of innovative Gen-IV nuclear fuel cycles imply fabricating host phases for actinide or mixed actinide compounds. Cubic stabilized zirconia (Zr, Y, Am)O(2-x) is one of the mixed phases tested in transmutation experiments. Wet chemical routes as an alternative to the powder metallurgy are being investigated to obtain the required phases while minimizing the handling of contaminating radioactive powder. Hydrolysis of zirconium, neodymium (a typical surrogate for americium) and yttrium in aqueous media in the presence of acetylacetone was firstly investigated. Progressive hydrolysis of zirconium acetylacetonate and sorption of trivalent cations and acacH on the zirconia particles led to a stable dispersion of nanoparticles (5-7 nm) in the 6-7 pH range. This sol gels with time or with temperature. The application to americium-containing solutions was then successfully tested: a stable sol was synthesized, characterized and used to prepare cubic stabilized zirconia (Zr, Y, Am)O(2-x).

  1. Stability and anti-glycation properties of intermediate moisture apple products fortified with green tea.

    Science.gov (United States)

    Lavelli, Vera; Corey, Mark; Kerr, William; Vantaggi, Claudia

    2011-07-15

    Intermediate moisture products made from blanched apple flesh and green tea extract (about 6mg of monomeric flavan 3-ols added per g of dry apple) or blanched apple flesh (control) were produced, and their quality attributes were investigated over storage for two months at water activity (a(w)) levels of 0.55 and 0.75, at 30°C. Products were evaluated for colour (L(∗), a(∗), and b(∗) Hunter's parameters), phytochemical contents (flavan 3-ols, chlorogenic acid, dihydrochalcones, ascorbic acid and total polyphenols), ferric reducing antioxidant potential, 2,2-diphenyl-1-(2,4,6-trinitrophenyl)hydrazyl radical-scavenging activity and ability to inhibit formation of fructose-induced advanced glycation end-products. During storage of the fortified and unfortified intermediate moisture apples, water availability was sufficient to support various chemical reactions involving phytochemicals, which degraded at different rates: ascorbic acid>flavan 3-ols>dihydrochalcones and chlorogenic acid. Colour variations occurred at slightly slower rates after green tea addition. In the intermediate moisture apple, antioxidant and anti-glycoxidative properties decreased at similar rates (half-life was about 80d at a(w) of 0.75, 30°C). In the green tea-fortified intermediate moisture apple, the antioxidant activity decreased at a slow rate (half-life was 165d at a(w) of 0.75, 30°C) and the anti-glycoxidative properties did not change, indicating that flavan 3-ol degradation involved the formation of derivatives that retained the properties of their parent compounds. Since these properties are linked to oxidative- and advanced glycation end-product-related diseases, these results suggest that green tea fortification of intermediate moisture apple products could be a valuable means of product innovation, to address consumers' nutritional needs. Copyright © 2011 Elsevier Ltd. All rights reserved.

  2. Structural and magnetic characterization of a tetranuclear copper(II) cubane stabilized by intramolecular metal cation-π interactions.

    Science.gov (United States)

    Papadakis, Raffaello; Rivière, Eric; Giorgi, Michel; Jamet, Hélène; Rousselot-Pailley, Pierre; Réglier, Marius; Simaan, A Jalila; Tron, Thierry

    2013-05-20

    A novel tetranuclear copper(II) complex (1) was synthesized from the self-assembly of copper(II) perchlorate and the ligand N-benzyl-1-(2-pyridyl)methaneimine (L(1)). Single-crystal X-ray diffraction studies revealed that complex 1 consists of a Cu4(OH)4 cubane core, where the four copper(II) centers are linked by μ3-hydroxo bridges. Each copper(II) ion is in a distorted square-pyramidal geometry. X-ray analysis also evidenced an unusual metal cation-π interaction between the copper ions and phenyl substituents of the ligand. Calculations based on the density functional theory method were used to quantify the strength of this metal-π interaction, which appears as an important stabilizing parameter of the cubane core, possibly acting as a driving parameter in the self-aggregation process. In contrast, using the ligand N-phenethyl-1-(2-pyridyl)methaneimine (L(2)), which only differs from L(1) by one methylene group, the same synthetic procedure led to a binuclear bis(μ-hydroxo)copper(II) complex (2) displaying intermolecular π-π interactions or, by a slight variation of the experimental conditions, to a mononuclear complex (3). These complexes were studied by X-ray diffraction techniques. The magnetic properties of complexes 1 and 2 are reported and discussed.

  3. New double-cation borohydrides

    Energy Technology Data Exchange (ETDEWEB)

    Lindemann, Inge; Domenech Ferrer, Roger; Schultz, Ludwig; Gutfleisch, Oliver [IFW Dresden, Institute for Metallic Materials, P.O. Box 270016, 01171 Dresden (Germany); Filinchuk, Yaroslav [Swiss-Norwegian Beam Lines at ESRF, BP-220, 38043 Grenoble (France); Hagemann, Hans; Cerny, Radovan [Department of Physical Chemistry and Crystallography, University of Geneva, 1211 Geneva (Switzerland)

    2011-07-01

    Complex hydrides are under consideration for on-board hydrogen storage due to their high hydrogen density. However, up to now conventional borohydrides are either too stable or unstable for applications as in PEM fuel cells (60-120 C). Recently, double-cation borohydride systems have attracted great interest. The desorption temperature of the borohydrides decreases with increasing electronegativity of the cation. Consequently, it is possible to tailor a feasible on-board hydrogen storage material by the combination of appropriate cations. The stability was found to be intermediate between the single-cation borohydride systems. Two combinations were sucessfully synthesised by metathesis reaction via high energy ball milling. Al-Li-borohydride shows desorption at about 70 C combined with a very high hydrogen density (17.2 wt.%) and the Na-Al-borohydride (14.2 wt.%) decomposes around 90 C. Both desorption temperatures are in the target range for applications. The decomposition pathways were observed by in-situ-Raman spectroscopy, DSC (Differential Scanning Calorimetry), TG (Thermogravimetry) and thermal desorption measurements.

  4. Alkaline cation complexing with calixarenes in electro-spray / mass spectrometry. Specificity for cesium, influence of solvation on ion species and radiolytic stability of the complexing media

    International Nuclear Information System (INIS)

    Allain, Francoise

    2000-01-01

    Radioactive waste management is a rather difficult issue. In order to reduce the volume of waste storage, particularly the Cs 135 (radioactive half-life 2.3 10 6 years), liquid-liquid extraction experiments have shown that crown calixarenes were able to selectively extract cesium cation in wastes. However, the stability under radiolysis of this type of macrocycle is unknown and is the theme of this thesis. Through the coupling of electro-spray and mass spectrometry, the selectivity of crown calixarenes for cesium has been confirmed. The necessity to optimize operating conditions during the utilization of this ionization mode was acknowledged for a correct interpretation of mass spectrum. The solvent nature, source temperature, applied voltage on the cone, gaseous phase stability and species ionization desorption rate are indeed parameters that should be taken into account. Experiments show that the solution species stability is inverse to the one in gaseous phase. In a solution, species stability is linked to the nature of the solvent (solvating power) whereas in gaseous phase, it is linked to the cationic affinity. In the current radiolysis conditions it has been demonstrated that calixarenes have a stable structure. Degradation products are very largely substitution products and do not hinder the caesium cation complexing. Concerning the quantitative aspect, an estimation was produced, however results are not satisfying: reference product synthesis is in fact necessary in order to establish calibration curves that will allow to precisely dose the various components derived from radiolysis [fr

  5. Effect of various intermediate ceramic layers on the interfacial stability of zirconia core and veneering ceramics.

    Science.gov (United States)

    Yoon, Hyung-In; Yeo, In-Sung; Yi, Yang-Jin; Kim, Sung-Hun; Lee, Jai-Bong; Han, Jung-Suk

    2015-01-01

    The purposes of this study were to evaluate the effects of intermediate ceramics on the adhesion between the zirconia core and veneer ceramics. The polished surfaces of fully sintered Y-TZP blocks received three different treatments: (1) connector (C), (2) liner (L) or (3) wash layer (W). All the treated zirconia blocks were veneered with either (a) fluorapatite glass-ceramic (E) or (b) feldspathic porcelain (V) and divided into four groups (CE, CV, LE and WV). For the control group, the testing surfaces of metal blocks were veneered with feldspathic porcelain (VM). A half of the samples in each group (n = 21) were exposed to thermocycling, while the other half of the specimens were stored at room temperature under dry conditions. All specimens were subjected to the shear test and the failed surfaces were microscopically examined. The elemental distribution at the zirconia core/veneer interface was analyzed. The specimens in Groups CE and CV exhibited significantly greater mean bond strength values than those in Groups LE and WV, respectively (p ceramic substances into the zirconia surface. A glass-ceramic based connector is significantly more favorable to core/veneer adhesion than the other intermediate ceramics evaluated in the study. However, thermal cycling affected the bond strength at the core/veneer interface differently according to the intermediate ceramics.

  6. The role of alkali metal cations in the stabilization of guanine quadruplexes: why K(+) is the best.

    Science.gov (United States)

    Zaccaria, F; Paragi, G; Fonseca Guerra, C

    2016-08-21

    The alkali metal ion affinity of guanine quadruplexes has been studied using dispersion-corrected density functional theory (DFT-D). We have done computational investigations in aqueous solution that mimics artificial supramolecular conditions where guanine bases assemble into stacked quartets as well as biological environments in which telomeric quadruplexes are formed. In both cases, an alkali metal cation is needed to assist self-assembly. Our quantum chemical computations on these supramolecular systems are able to reproduce the experimental order of affinity of the guanine quadruplexes for the cations Li(+), Na(+), K(+), Rb(+), and Cs(+). The strongest binding is computed between the potassium cation and the quadruplex as it occurs in nature. The desolvation and the size of alkali metal cations are thought to be responsible for the order of affinity. Until now, the relative importance of these two factors has remained unclear and debated. By assessing the quantum chemical 'size' of the cation, determining the amount of deformation of the quadruplex needed to accommodate the cation and through the energy decomposition analysis (EDA) of the interaction energy between the cation and the guanines, we reveal that the desolvation and size of the alkali metal cation are both almost equally responsible for the order of affinity.

  7. Anaerobic stabilization and conversion of transformed intermediates of antibiotic pharmaceutical effluent in a fluidized bed reactor.

    Science.gov (United States)

    Tamijevendane, S; Saravanane, R; Rajesh, R; Sivacoumar, R

    2011-07-01

    The formulation and implementation of regulatory standards for the ultimate disposal and reuse of transformed products of antibiotic drugs and solvents have been a pending issue in the waste management of pharmaceutical industries especially in the developing countries like India. A case study has been identified and the current issues in one of the major pharmaceutical industry (manufacturing cephalosporin drugs) located in Chennai, India, has been discussed for the possible implementation of anaerobically transformed intermediates of antibiotic pharmaceutical waste sludge. The objective of the study was to determine the effect of bioaugmentation on the convertibility of anaerobically transformed intermediates of antibiotic pharmaceutical waste sludge into residuals and biocompost. Cephalosporin is a common name refers to cephradine (C16H19N3O4S) and cephalexin (C16H17N3O4S.H2O). Based on the critical examination of results, the industry is looking for the alternatives of either direct disposal of 7-amino-3-deacetoxycephalosporanic acid (7-ADCA) and phenyl acetic acid or for further degradation and disposal, which will essentially require additional cost and maintenance. The present regulatory standard implemented in India does not envisage such disposal alternatives and hence this would invite suggestions and recommendations of the expertise for the possible implementation on the pending issue in the antibiotic based pharmaceutical industries. The presence of cephalosporin increases total strength (Chemical Oxygen Demand) of the effluent and indirectly increases the cost of the treatment. Hence the biotransformation of cephalosporin either alone or in combination with other energetic compounds, offers the potential for an economical and environment friendly disposal alternative for the anaerobically transformed intermediates of antibiotic pharmaceutical waste sludge.

  8. Production of nuclei far from the beta stability line using intermediate-energy heavy ions

    International Nuclear Information System (INIS)

    Guerreau, D.

    1986-05-01

    The production of far unstable nuclei using heavy ion accelerators in the intermediate energy domain is reviewed. The various mechanisms responsible for the production of exotic species, mainly the projectile fragmentation and transfer reactions, are discussed, and the first experimental results presented. Results can be summarized as follows: existence of 4 new isotopes 22 C, 23 N, 29 Ne, 30 Ne; indication of bound character of 71 Ni, 72 Ni; clear evidence for bound character of 23 Si, 27 S, 31 Ar, 35 Ca; indications of bound character of 43 V, 46 Mn, 47 Mn, 48 Fe, 50 Co, 52 Co, 52 Ni, 55 Cu, 56 Cu

  9. Emergence and stability of intermediate open vesicles in disk-to-vesicle transitions.

    Science.gov (United States)

    Li, Jianfeng; Zhang, Hongdong; Qiu, Feng; Shi, An-Chang

    2013-07-01

    The transition between two basic structures, a disk and an enclosed vesicle, of a finite membrane is studied by examining the minimum energy path (MEP) connecting these two states. The MEP is constructed using the string method applied to continuum elastic membrane models. The results reveal that, besides the commonly observed disk and vesicle, open vesicles (bowl-shaped vesicles or vesicles with a pore) can become stable or metastable shapes. The emergence, stability, and probability distribution of these open vesicles are analyzed. It is demonstrated that open vesicles can be stabilized by higher-order elastic energies. The estimated probability distribution of the different structures is in good agreement with available experiments.

  10. Use of the cation exchange equilibrium method for the determination of stability constants of Co(II) with soil humic and fulvic acids

    International Nuclear Information System (INIS)

    Du, J.Z.; Zhou, C.Y.; Dong, W.M.; Tao, Z.Y.

    1999-01-01

    The stability constants for tracer concentrations of Co(II) complexes with both the red earth humic and fulvic acids were determined at pH 5.9 and ionic strength 0.010 mol/l by using the ARDAKANI-STEVENSON cation exchange equilibrium method and the radiotracer 60 Co. It was found that the 1:1 complexes of Co(II) with the red earth humic and fulvic acids were formed and that the average values of logβ (stability constant) of humic and fulvic acid complexes were 5.76±0.19 and 4.42±0.03, respectively. (author)

  11. Engineering of CH 3 NH 3 PbI 3 Perovskite Crystals by Alloying Large Organic Cations for Enhanced Thermal Stability and Transport Properties

    KAUST Repository

    Peng, Wei

    2016-07-28

    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.

  12. Engineering of CH 3 NH 3 PbI 3 Perovskite Crystals by Alloying Large Organic Cations for Enhanced Thermal Stability and Transport Properties

    KAUST Repository

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

    2016-01-01

    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.

  13. Factors Affecting Impact Toughness in Stabilized Intermediate Purity 21Cr Ferritic Stainless Steels and Their Simulated Heat-Affected Zones

    Science.gov (United States)

    Anttila, Severi; Alatarvas, Tuomas; Porter, David A.

    2017-12-01

    The correlation between simulated weld heat-affected zone microstructures and toughness parameters has been investigated in four intermediate purity 21Cr ferritic stainless steels stabilized with titanium and niobium either separately or in combination. Extensive Charpy V impact toughness testing was carried out followed by metallography including particle analysis using electron microscopy. The results confirmed that the grain size and the number density of particle clusters rich in titanium nitride and carbide with an equivalent circular diameter of 2 µm or more are statistically the most critical factors influencing the ductile-to-brittle transition temperature. Other inclusions and particle clusters, as well as grain boundary precipitates, are shown to be relatively harmless. Stabilization with niobium avoids large titanium-rich inclusions and also suppresses excessive grain growth in the heat-affected zone when reasonable heat inputs are used. Thus, in order to maximize the limited heat-affected zone impact toughness of 21Cr ferritic stainless steels containing 380 to 450 mass ppm of interstitials, the stabilization should be either titanium free or the levels of titanium and nitrogen should be moderated.

  14. Power Output Stability Research for Harvesting Automobile Exhaust Energy with Heat Capacity Material as Intermediate Medium

    Science.gov (United States)

    Xiao, Longjie; He, Tianming; Mei, Binyu; Wang, Yiping; Wang, Zongsong; Tan, Gangfeng

    2018-06-01

    Automobile exhaust energy thermoelectric utilization can promote energy-saving and emission-reduction. Unexpected urban traffic conditions lead to the hot-end temperature instability of the exhaust pipe-mounted thermoelectric generator (TEG), and influence the TEG power generation efficiency. The heat conduction oil circulation located at the hot-end could smooth the temperature fluctuation, at the expense of larger system size and additional energy supply. This research improves the TEG hot-end temperature stability by installing solid heat capacity material (SHCM) to the area between the outer wall of the exhaust pipe and the TEG, which has the merits of simple structure, light weight and no additional energy consumption. The exhaust temperature and flow rate characteristics with various driving conditions are firstly studied for the target engine. Then the convective heat transfer models of SHCM's hot-end and thermoelectric material's cold-end are established. Meanwhile, SHCM thermal properties' effects on the amplitude and response speed of the TEG hot-end temperature are studied. The candidate SHCM with the characteristics of low thermal resistance and high heat capacity is determined. And the heat transfer model going through from TEG's hot-end to the cold-end is established. The results show that the SHCM significantly improves the TEG hot-end temperature stability but slightly reduces the average power output. When the engine working conditions change a lot, the SHCM's improvement on the TEG hot-end temperature stability is more significant, but the reduction of the average power output becomes more remarkable.

  15. Factors that impact the stability of vitamin C at intermediate temperatures in a food matrix.

    Science.gov (United States)

    Herbig, Anna-Lena; Renard, Catherine M G C

    2017-04-01

    The study comprises a systematic and quantitative evaluation of potential intrinsic and extrinsic factors that impact vitamin C degradation in a real food matrix. The supernatant of centrifuged apple purée was fortified in vitamin C, and degradation was followed without stirring. Model discrimination indicated better fit for the zero order model than the first order model which was hence chosen for determination of rate constants. pH influenced strongly vitamin C degradation in citrate-phosphate buffer but not in the apple purée serum. To get an idea of the impact of the food matrix, stability in apple purée serum was compared with that in carrot purée. In the latter, stability was slightly higher. Vitamin C degradation rates were not influenced by its initial concentration. The temperature effect was only marked in the temperature range 40-60°C. In the range 60-80°C, filling height of tubes had the greatest impact. Copyright © 2016 Elsevier Ltd. All rights reserved.

  16. Effect of dysprosia doping on structural and electrical property of stabilized zirconia for intermediate- temperature SOFCs

    International Nuclear Information System (INIS)

    Pastor, M.; Maiti, S.; Pandey, A.; Biswas, K.; Manna, I.

    2011-01-01

    Present work deals with structural, micro-structural and electrical properties of dysprosia stabilized zirconia electrolyte, which have been evaluated by means of X-ray diffraction (XRD) and scanning (SEM), and complex impedance analysis respectively. The amount of dysprosia was varied from 2 to 12 mol% in zirconia. The addition of dysprosia (8-12 mol%) stabilized the cubic zirconia phase, which was analyzed from XRD analysis. SEM micrographs clearly showed the improvement in sinterability with increase in dysprosia concentration up to 6 mol% disprosia. Complex impedance analysis was performed in the temperature range from 250 to 600 deg. C. The results indicated a gradual decrease in impedance of both bulk and grain boundary and increase in conductivity with dysprosia doping up to 6 mol% and thereafter showing a reverse trend. The activation energies for oxygen ion migration were also found to decrease with increase in dysprosia doping which was in the range of 0.99 - 1.28 eV. The average thermal expansion coefficient increases linearly.

  17. Exceptional power density and stability at intermediate temperatures in protonic ceramic fuel cells

    Science.gov (United States)

    Choi, Sihyuk; Kucharczyk, Chris J.; Liang, Yangang; Zhang, Xiaohang; Takeuchi, Ichiro; Ji, Ho-Il; Haile, Sossina M.

    2018-03-01

    Over the past several years, important strides have been made in demonstrating protonic ceramic fuel cells (PCFCs). Such fuel cells offer the potential of environmentally sustainable and cost-effective electric power generation. However, their power outputs have lagged behind predictions based on their high electrolyte conductivities. Here we overcome PCFC performance and stability challenges by employing a high-activity cathode, PrBa0.5Sr0.5Co1.5Fe0.5O5+δ (PBSCF), in combination with a chemically stable electrolyte, BaZr0.4Ce0.4Y0.1Yb0.1O3 (BZCYYb4411). We deposit a thin dense interlayer film of the cathode material onto the electrolyte surface to mitigate contact resistance, an approach which is made possible by the proton permeability of PBSCF. The peak power densities of the resulting fuel cells exceed 500 mW cm-2 at 500 °C, while also offering exceptional, long-term stability under CO2.

  18. Surface Ligand Promotion of Carbon Dioxide Reduction through Stabilizing Chemisorbed Reactive Intermediates.

    Science.gov (United States)

    Wang, Zhijiang; Wu, Lina; Sun, Kun; Chen, Ting; Jiang, Zhaohua; Cheng, Tao; Goddard, William A

    2018-05-23

    We have explored functionalizing metal catalysts with surface ligands as an approach to facilitate electrochemical carbon dioxide reduction reaction (CO 2 RR). To provide a molecular level understanding of the mechanism by which this enhancement occurs, we combine in situ spectroscopy analysis with an interpretation based on quantum mechanics (QM) calculations. We find that a surface ligand can play a critical role in stabilizing the chemisorbed CO 2 , which facilitates CO 2 activation and leads to a 0.3 V decrease in the overpotential for carbon monoxide (CO) formation. Moreover, the presence of the surface ligand leads to nearly exclusive CO production. At -0.6 V (versus reversible hydrogen electrode, RHE), CO is the only significant product with a faradic efficiency of 93% and a current density of 1.9 mA cm -2 . This improvement corresponds to 53-fold enhancement in turnover frequency compared with the Ag nanoparticles (NPs) without surface ligands.

  19. Cation-pi interactions stabilize the structure of the antimicrobial peptide indolicidin near membranes: molecular dynamics simulations

    DEFF Research Database (Denmark)

    Khandelia, Himanshu; Kaznessis, Yiannis N

    2007-01-01

    We implemented molecular dynamics simulations of the 13-residue antimicrobial peptide indolicidin (ILPWKWPWWPWRR-NH2) in dodecylphosphocholine (DPC) and sodium dodecyl sulfate (SDS) micelles. In DPC, a persistent cation-pi interaction between TRP11 and ARG13 defined the structure of the peptide...... near the interface. A transient cation-pi interaction was also observed between TRP4 and the choline group on DPC lipids. We also implemented simulation of a mutant of indolicidin in the DPC micelle where TRP11 was replaced by ALA11. As a result of the mutation, the boat-shaped conformation is lost...... and the structure becomes significantly less defined. On the basis of this evidence, we argue that cation-pi interactions determine the experimentally measured, well-defined boat-shaped structure of indolicidin. In SDS, the lack of such interactions and the electrostatic binding of the terminal arginine residues...

  20. Atomistic structural ensemble refinement reveals non-native structure stabilizes a sub-millisecond folding intermediate of CheY

    International Nuclear Information System (INIS)

    Shi, Jade; Schwantes, Christian; Bilsel, Osman

    2017-01-01

    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. 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. The resulting 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. We then predict incisive single molecule FRET experiments, using these results, as a means of model validation. Our 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.

  1. Actinide cation-cation complexes

    International Nuclear Information System (INIS)

    Stoyer, N.J.; Seaborg, G.T.

    1994-12-01

    The +5 oxidation state of U, Np, Pu, and Am is a linear dioxo cation (AnO 2 + ) with a formal charge of +1. These cations form complexes with a variety of other cations, including actinide cations. Other oxidation states of actinides do not form these cation-cation complexes with any cation other than AnO 2 + ; therefore, cation-cation complexes indicate something unique about AnO 2 + cations compared to actinide cations in general. The first cation-cation complex, NpO 2 + ·UO 2 2+ , was reported by Sullivan, Hindman, and Zielen in 1961. Of the four actinides that form AnO 2 + species, the cation-cation complexes of NpO 2 + have been studied most extensively while the other actinides have not. The only PuO 2 + cation-cation complexes that have been studied are with Fe 3+ and Cr 3+ and neither one has had its equilibrium constant measured. Actinides have small molar absorptivities and cation-cation complexes have small equilibrium constants; therefore, to overcome these obstacles a sensitive technique is required. Spectroscopic techniques are used most often to study cation-cation complexes. Laser-Induced Photacoustic Spectroscopy equilibrium constants for the complexes NpO 2 + ·UO 2 2+ , NpO 2 + ·Th 4+ , PuO 2 + ·UO 2 2+ , and PuO 2 + ·Th 4+ at an ionic strength of 6 M using LIPAS are 2.4 ± 0.2, 1.8 ± 0.9, 2.2 ± 1.5, and ∼0.8 M -1

  2. 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

    International Nuclear Information System (INIS)

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

    1981-06-01

    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 0 C. This may restrict allowable gross thermal loadings in waste repositories in volcanic rocks

  3. Isomerization of propargyl cation to cyclopropenyl cation ...

    Indian Academy of Sciences (India)

    step) for isomeri- zation of the linear propargyl cation to ..... C3, C4 and C5. The ZPE corrections in each case are derived from the. B3LYP calculations. ..... the converse of which gives the relative capacity of the. LPD's to stabilize TS6 with respect ...

  4. 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

    2014-02-01

    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.

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

    Science.gov (United States)

    Hüttel, Wolfgang; Spencer, Jonathan B; Leadlay, Peter F

    2014-01-01

    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.

  6. Intermediate-term medium-range earthquake prediction algorithm M8: A new spatially stabilized application in Italy

    International Nuclear Information System (INIS)

    Romashkova, L.L.; Kossobokov, V.G.; Peresan, A.; Panza, G.F.

    2001-12-01

    A series of experiments, based on the intermediate-term earthquake prediction algorithm M8, has been performed for the retrospective simulation of forward predictions in the Italian territory, with the aim to design an experimental routine for real-time predictions. These experiments evidenced two main difficulties for the application of M8 in Italy. The first one is due to the fact that regional catalogues are usually limited in space. The second one concerns certain arbitrariness and instability, with respect to the positioning of the circles of investigation. Here we design a new scheme for the application of the algorithm M8, which is less subjective and less sensitive to the position of the circles of investigation. To perform this test, we consider a recent revision of the Italian catalogue, named UCI2001, composed by CCI1996, NEIC and ALPOR data for the period 1900-1985, and updated with the NEIC reduces the spatial heterogeneity of the data at the boundaries of Italy. The new variant of the M8 algorithm application reduces the number of spurious alarms and increases the reliability of predictions. As a result, three out of four earthquakes with magnitude M max larger than 6.0 are predicted in the retrospective simulation of the forward prediction, during the period 1972-2001, with a space-time volume of alarms comparable to that obtained with the non-stabilized variant of the M8 algorithm in Italy. (author)

  7. Catecholase activity of dicopper(II)-bispidine complexes: stabilities and structures of intermediates, kinetics and reaction mechanism.

    Science.gov (United States)

    Born, Karin; Comba, Peter; Daubinet, André; Fuchs, Alexander; Wadepohl, Hubert

    2007-01-01

    A mechanism for the oxidation of 3,5-di-tert-butylcatechol (dtbc) with dioxygen to the corresponding quinone (dtbq), catalyzed by bispidine-dicopper complexes (bispidines are various mono- and dinucleating derivatives of 3,7-diazabicyclo[3.3.1]nonane with bis-tertiary-amine-bispyridyl or bis-tertiary-amine-trispyridyl donor sets), is proposed on the basis of (1) the stoichiometry of the reaction as well as the stabilities and structures [X-ray, density functional theory (B3LYP, TZV)] of the bispidine-dicopper(II)-3,4,5,6-tetrachlorcatechol intermediates, (2) formation kinetics and structures (molecular mechanics, MOMEC) of the end-on peroxo-dicopper(II) complexes and (3) kinetics of the stoichiometric (anaerobic) and catalytic (aerobic) copper-complex-assisted oxidation of dtbc. This involves (1) the oxidation of the dicopper(I) complexes with dioxygen to the corresponding end-on peroxo-dicopper(II) complexes, (2) coordination of dtbc as a bridging ligand upon liberation of H(2)O(2) and (3) intramolecular electron transfer to produce dtbq, which is liberated, and the dicopper(I) catalyst. Although the bispidine complexes have reactivities comparable to those of recently published catalysts with macrocyclic ligands, which seem to reproduce the enzyme-catalyzed process in various reaction sequences, a strikingly different oxidation mechanism is derived from the bispidine-dicopper-catalyzed reaction.

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

    Science.gov (United States)

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

    2012-08-07

    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.

  9. Formulation and Stabilization of Concentrated Edible Oil-in-Water Emulsions Based on Electrostatic Complexes of a Food-Grade Cationic Surfactant (Ethyl Lauroyl Arginate) and Cellulose Nanocrystals.

    Science.gov (United States)

    Bai, Long; Xiang, Wenchao; Huan, Siqi; Rojas, Orlando J

    2018-05-14

    We report on high-internal-phase, oil-in-water Pickering emulsions that are stable against coalescence during storage. Viscous, edible oil (sunflower) was emulsified by combining naturally derived cellulose nanocrystals (CNCs) and a food-grade, biobased cationic surfactant obtained from lauric acid and L-arginine (ethyl lauroyl arginate, LAE). The interactions between CNC and LAE were elucidated by isothermal titration calorimetry (ITC) and supplementary techniques. LAE adsorption on CNC surfaces and its effect on nanoparticle electrostatic stabilization, aggregation state, and emulsifying ability was studied and related to the properties of resultant oil-in-water emulsions. Pickering systems with tunable droplet diameter and stability against oil coalescence during long-term storage were controllably achieved depending on LAE loading. The underlying stabilization mechanism was found to depend on the type of complex formed, the LAE structures adsorbed on the cellulose nanoparticles (as unimer or as adsorbed admicelles), the presence of free LAE in the aqueous phase, and the equivalent alkane number of the oil phase (sunflower and dodecane oils were compared). The results extend the potential of CNC in the formulation of high-quality and edible Pickering emulsions. The functional properties imparted by LAE, a highly effective molecule against food pathogens and spoilage organisms, open new opportunities in food, cosmetics, and pharmaceutical applications, where the presence of CNC plays a critical role in achieving synergistic effects with LAE.

  10. GAS PHASE STRUCTURE AND STABILITY OF COMPLEX FORMED BY H2O, NH3, H2S AND THEIR METHYL DERIVATIVES WITH THE CATION CO2+

    Directory of Open Access Journals (Sweden)

    Cahyorini Kusumawardani

    2010-06-01

    Full Text Available Ab initio molecular orbital calculations at the Hartree-Fock-Self Consistent Field (HF-SCF have been performed in order to determine the structure and gas phase energies of complex formed by the Lewis bases of H2O, NH3, H2S and their methyl derivatives with the cation Co2+. The relative basicities of the base studied depend on both the substituent. The gas-phase interaction energies computed by the SCF method including electron correlation Møller-Plesset 2 (MP2 dan Configuration Iteration (CI were comparable in accuracy. The binding energies computed by these two methods reach the targeted chemical accuracy.   Keywords: ab initio calculation, cobalt complex, structure stability

  11. Computational and experimental studies on stabilities, reactions and reaction rates of cations and ion-dipole complexes

    NARCIS (Netherlands)

    Ervasti, H.K.

    2008-01-01

    In this thesis, ion stability, ion-molecule reactions and reaction rates are studied using mass spectrometry and molecular modelling. In Chapter 2 the effect of functional group substitution on neutral and ionised ketene are studied. Electron-donating substituents show a stabilising positive

  12. Formulation, optimization and characterization of cationic polymeric nanoparticles of mast cell stabilizing agent using the Box-Behnken experimental design.

    Science.gov (United States)

    Gajra, Balaram; Patel, Ravi R; Dalwadi, Chintan

    2016-01-01

    The present research work was intended to develop and optimize sustained release of biodegradable chitosan nanoparticles (CSNPs) as delivery vehicle for sodium cromoglicate (SCG) using the circumscribed Box-Behnken experimental design (BBD) and evaluate its potential for oral permeability enhancement. The 3-factor, 3-level BBD was employed to investigate the combined influence of formulation variables on particle size and entrapment efficiency (%EE) of SCG-CSNPs prepared by ionic gelation method. The generated polynomial equation was validated and desirability function was utilized for optimization. Optimized SCG-CSNPs were evaluated for physicochemical, morphological, in-vitro characterizations and permeability enhancement potential by ex-vivo and uptake study using CLSM. SCG-CSNPs exhibited particle size of 200.4 ± 4.06 nm and %EE of 62.68 ± 2.4% with unimodal size distribution having cationic, spherical, smooth surface. Physicochemical and in-vitro characterization revealed existence of SCG in amorphous form inside CSNPs without interaction and showed sustained release profile. Ex-vivo and uptake study showed the permeability enhancement potential of CSNPs. The developed SCG-CSNPs can be considered as promising delivery strategy with respect to improved permeability and sustained drug release, proving importance of CSNPs as potential oral delivery system for treatment of allergic rhinitis. Hence, further studies should be performed for establishing the pharmacokinetic potential of the CSNPs.

  13. Role of the reaction of stabilized Criegee intermediates with peroxy radicals in particle formation and growth in air.

    Science.gov (United States)

    Zhao, Yue; Wingen, Lisa M; Perraud, Véronique; Greaves, John; Finlayson-Pitts, Barbara J

    2015-05-21

    Ozonolysis of alkenes is an important source of secondary organic aerosol (SOA) in the atmosphere. However, the mechanisms by which stabilized Criegee intermediates (SCI) react to form and grow the particles, and in particular the contributions from oligomers, are not well understood. In this study, ozonolysis of trans-3-hexene (C6H12), as a proxy for small alkenes, was investigated with an emphasis on the mechanisms of particle formation and growth. Ozonolysis experiments were carried out both in static Teflon chambers (18-20 min reaction times) and in a glass flow reactor (24 s reaction time) in the absence and presence of OH or SCI scavengers, and under different relative humidity (RH) conditions. The chemical composition of polydisperse and size-selected SOA particles was probed using different mass spectrometric techniques and infrared spectroscopy. Oligomers having SCI as the chain unit are found to be the dominant components of such SOA particles. The formation mechanism for these oligomers suggested by our results follows the sequential addition of SCI to organic peroxy (RO2) radicals, in agreement with previous studies by Moortgat and coworkers. Smaller particles are shown to have a relatively greater contribution from longer oligomers. Higher O/C ratios are observed in smaller particles and are similar to those of oligomers resulting from RO2 + nSCI, supporting a significant role for longer oligomers in particle nucleation and early growth. Under atmospherically relevant RH of 30-80%, water vapor suppresses oligomer formation through scavenging SCI, but also enhances particle nucleation. Under humid conditions, or in the presence of formic or hydrochloric acid as SCI scavengers, peroxyhemiacetals are formed by the acid-catalyzed particle phase reaction between oligomers from RO2 + nSCI and a trans-3-hexene derived carbonyl product. In contrast to the ozonolysis of trans-3-hexene, oligomerization involving RO2 + nSCI does not appear to be prevalent in the

  14. Stability and aggregation of nanoscale titanium dioxide particle (nTiO2): Effect of cation valence, humic acid, and clay colloids.

    Science.gov (United States)

    Tang, Zhong; Cheng, Tao

    2018-02-01

    Fate and transport of engineered nanoscale titanium dioxide (nTiO 2 ) have received much attention during the past decade. The aggregation and stability of nTiO 2 in water with complicated components, however, have not been fully examined. The objective of this paper is to determine the individual and synergistic effect of cation valence, humic acid, and clay colloids on nTiO 2 stability and aggregation, and elucidate the related mechanisms. We conducted systematic laboratory experiments to determine nTiO 2 stability and aggregation in NaCl and MgCl 2 solutions, both in the absence and presence of humic acid and illite colloids. Results showed that Mg 2+ , in comparison to Na + , could make the zeta potential of nTiO 2 more positive, and shift the point of zero charge of nTiO 2 (pH pzc,TiO2 ) towards higher pH. We also found that nTiO 2 are destabilized by illite colloids at pH < pH pzc,TiO2 through formation of illite-nTiO 2 hetero-aggregates, but are not interfered by illite colloids at higher pH. HA was found to make nTiO 2 stable via electrostatic and steric effects, both in the absence and presence of illite colloids. Calculated interaction energy based on DLVO theory revealed that instability of the nTiO 2 suspensions is mainly caused by primary minima, and that secondary minima normally do not destabilize the suspension, even though they are found to promote aggregation. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Molecular complexation of curcumin with pH sensitive cationic copolymer enhances the aqueous solubility, stability and bioavailability of curcumin.

    Science.gov (United States)

    Kumar, Sunny; Kesharwani, Siddharth S; Mathur, Himanshi; Tyagi, Mohit; Bhat, G Jayarama; Tummala, Hemachand

    2016-01-20

    Curcumin is a natural dietary compound with demonstrated potential in preventing/treating several chronic diseases in animal models. However, this success is yet to be translated to humans mainly because of its poor oral bioavailability caused by extremely low water solubility. This manuscript demonstrates that water insoluble curcumin (~1μg/ml) forms highly aqueous soluble complexes (>2mg/ml) with a safe pH sensitive polymer, poly(butyl-methacrylate-co-(2-dimethylaminoethyl) methacrylate-co-methyl-methacrylate) when precipitated together in water. The complexation process was optimized to enhance curcumin loading by varying several formulation factors. Acetone as a solvent and polyvinyl alcohol as a stabilizer with 1:2 ratio of drug to polymer yielded complexes with relatively high loading (~280μg/ml) and enhanced solubility (>2mg/ml). The complexes were amorphous in solid and were soluble only in buffers with pHs less than 5.0. Hydrogen bond formation and hydrophobic interactions between curcumin and the polymer were recorded by infrared spectroscopy and nuclear magnetic resonance spectroscopy, respectively. Molecular complexes of curcumin were more stable at various pHs compared to unformulated curcumin. In mice, these complexes increased peak plasma concentration of curcumin by 6 times and oral bioavailability by ~20 times. This is a simple, economic and safer strategy of enhancing the oral bioavailability of curcumin. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. Diarylhalotelluronium(IV) cations [(8-Me2NC10H6)2TeX]+ (X = Cl, Br, I) stabilized by intramolecularly coordinating N-donor substituents.

    Science.gov (United States)

    Beckmann, Jens; Bolsinger, Jens; Duthie, Andrew; Finke, Pamela

    2013-09-14

    The stoichiometrically controlled halogenation of the intramolecularly coordinated diaryltelluride (8-Me2NC10H6)2Te using SO2Cl2, Br2 and I2 was studied. At an equimolar ratio, the diarylhalotelluronium cations [(8-Me2NC10H6)2TeX](+) (1, X = Cl; 2, X = Br; 3, X = I) formed and were isolated as 1·Cl(-)·H2O·1/2THF, 2·Br(-), and 3·I(-), respectively. When the same reactions were carried out in the presence of KPF6, 1·PF6(-) and 22·Br(-)·PF6(-) were obtained. The chlorination of (8-Me2NC10H6)2Te with an excess of SO2Cl2 occurred with a double electrophilic substitution at the 8-dimethylaminonaphthyl residues (in the ortho- and para-positions) and afforded the diaryltellurium dichloride (5,7-Cl2-8-Me2NC10H4)2TeCl2 (4). The bromination of (8-Me2NC10H6)2Te with three equivalents of Br2 took place with a single electrophilic substitution at the 8-dimethylaminonaphthyl residues (in the para-positions) and provided the diaryltellurium dibromide (5-Br-8-Me2NC10H5)2TeBr2 (5), while an excess of Br2 produced the diarylbromotelluronium cation [(5-Br-8-Me2NC10H5)2TeBr](+) (6) that was isolated as 6·Br3(-). The reaction of (8-Me2NC10H6)2Te with two or three equivalents of iodine provided 3·I3(-) and 3·I3(-)·I2, respectively. In the presence of water, 1·Cl(-)·H2O·1/2THF, 2·Br(-), 3·I(-) and 3·I3(-) hydrolyzed to give the previously known diarylhydroxytelluronium cation [(8-Me2NC10H6)2TeOH](+) (7) that was isolated as 7·Cl(-), 7·Br(-)·H2O·THF, 7·I(-) and 7·I3(-)·H2O, respectively. The molecular structures of 1-7 were investigated in the solid-state by (125)Te MAS NMR spectroscopy and X-ray crystallography and in solution by multinuclear NMR spectroscopy ((1)H, (13)C, (125)Te), electrospray mass spectrometry and conductivity measurements. The stabilization of cations 1-3 by the intramolecular coordination was estimated by DFT calculations at the B3PW91/TZ level of theory.

  17. 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

    2013-01-01

    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.

  18. Stopped Flow Kinetics of MnII Catalysed Periodate Oxidation of 2, 3- dimethylaniline - Evaluation of Stability Constant of the Ternary Intermediate Complex

    Directory of Open Access Journals (Sweden)

    Rajneesh Dutt Kaushik

    2015-03-01

    Full Text Available The formation of ternary intermediate unstable complex during the oxidation of aromatic amines by periodate ion catalysed by MnII has been proposed in case of some anilines. This paper is the first report on stopped-flow kinetic study and evaluation of stability constant of ternary complex forming in the MnII - catalysed periodate oxidation of 2, 3-dimethylaniline (D in acetone-water medium. Stop-flow spectrophotometric method was used to study the ternary complex formation and to determine its stability constant. The stop-flow trace shows the reaction to occur in two steps. The first step, which is presumably the formation of ternary complex, is relatively fast while the second stage is relatively quite slow. The stability constant evaluated for D - MnII - IO4- ternary complex by determining  equilibrium absorbance is (2.2 ± 1.0 × 105. Kinetics of ternary complex formation was defined by the rate law(A  under pseudo first order conditions. ln{[C2]eq / ( [C2]eq -[C2]} = kobs . t (A where, kobs is the pseudo first order rate constant, [C2] is concentration of ternary complex at given time t, and [C2]eq is the equilibrium concentration of ternary complex. © 2015 BCREC UNDIP. All rights reservedReceived: 3rd October 2014; Revised: 4th December 2014; Accepted: 15th December 2014How to Cite: Kaushik, R.D., Agarwal, R., Tyagi, P., Singh, O., Singh, J. (2015. Stopped Flow Kinetics of MnII Catalysed Periodate Oxidation of 2,3-dimethylaniline - Evaluation of Stability Constant of the Ternary Intermediate Complex. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (1: 78-87. (doi:10.9767/bcrec.10.1.7621.78-87Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.1.7621.78-87

  19. The effects of monovalent and divalent cations on the stability of silver nanoparticles formed from direct reduction of silver ions by Suwannee River humic acid/natural organic matter

    Energy Technology Data Exchange (ETDEWEB)

    Akaighe, Nelson [Chemistry Department, Florida Institute of Technology, 150 West University Boulevard, Melbourne, FL 32901 (United States); Depner, Sean W.; Banerjee, Sarbajit [Department of Chemistry, 410 Natural Sciences Complex, University at Buffalo, The State University of New York, Buffalo, NY 14260-3000 (United States); Sharma, Virender K. [Chemistry Department, Florida Institute of Technology, 150 West University Boulevard, Melbourne, FL 32901 (United States); Sohn, Mary, E-mail: msohn@fit.edu [Chemistry Department, Florida Institute of Technology, 150 West University Boulevard, Melbourne, FL 32901 (United States)

    2012-12-15

    The formation and characterization of AgNPs (silver nanoparticles) formed from the reduction of Ag{sup +} by SRNOM (Suwannee River natural organic matter) is reported. The images of SRNOM-formed AgNPs and the selected area electron diffraction (SAED) were captured by high resolution transmission electron microscopy (HRTEM). The colloidal and chemical stability of SRNOM- and SRHA (Suwannee River humic acid)-formed AgNPs in different ionic strength solutions of NaCl, KCl, CaCl{sub 2} and MgCl{sub 2} was investigated in an effort to evaluate the key fate and transport processes of these nanoparticles in natural aqueous environments. The aggregation state, stability and sedimentation rate of the AgNPs were monitored by Dynamic Light Scattering (DLS), zeta potential, and UV-vis measurements. The results indicate that both types of AgNPs are very unstable in high ionic strength solutions. Interestingly, the nanoparticles appeared more unstable in divalent cation solutions than in monovalent cation solutions at similar concentrations. Furthermore, the presence of SRNOM and SRHA contributed to the nanoparticle instability at high ionic strength in divalent metallic cation solutions, most likely due to intermolecular bridging with the organic matter. The results clearly suggest that changes in solution chemistry greatly affect nanoparticle long term stability and transport in natural aqueous environments. Highlights: Black-Right-Pointing-Pointer Formation of SRNOM-AgNPs under environmentally relevant conditions Black-Right-Pointing-Pointer Influence of monovalent versus divalent cations on SRHA- and SRNOM-AgNP stability Black-Right-Pointing-Pointer Effect of AgNPs on organic matter removal from water columns.

  20. Cation radicals of xanthophylls.

    Science.gov (United States)

    Galinato, Mary Grace I; Niedzwiedzki, Dariusz; Deal, Cailin; Birge, Robert R; Frank, Harry A

    2007-10-01

    Carotenes and xanthophylls are well known to act as electron donors in redox processes. This ability is thought to be associated with the inhibition of oxidative reactions in reaction centers and light-harvesting pigment-protein complexes of photosystem II (PSII). In this work, cation radicals of neoxanthin, violaxanthin, lutein, zeaxanthin, beta-cryptoxanthin, beta-carotene, and lycopene were generated in solution using ferric chloride as an oxidant and then studied by absorption spectroscopy. The investigation provides a view toward understanding the molecular features that determine the spectral properties of cation radicals of carotenoids. The absorption spectral data reveal a shift to longer wavelength with increasing pi-chain length. However, zeaxanthin and beta-cryptoxanthin exhibit cation radical spectra blue-shifted compared to that of beta-carotene, despite all of these molecules having 11 conjugated carbon-carbon double bonds. CIS molecular orbital theory quantum computations interpret this effect as due to the hydroxyl groups in the terminal rings selectively stabilizing the highest occupied molecular orbitals of preferentially populated s-trans-isomers. The data are expected to be useful in the analysis of spectral results from PSII pigment-protein complexes seeking to understand the role of carotene and xanthophyll cation radicals in regulating excited state energy flow, in protecting PSII reaction centers against photoinhibition, and in dissipating excess light energy absorbed by photosynthetic organisms but not used for photosynthesis.

  1. Effector region of the translation elongation factor EF-Tu.GTP complex stabilizes an orthoester acid intermediate structure of aminoacyl-tRNA in a ternary complex.

    Science.gov (United States)

    Förster, C; Limmer, S; Zeidler, W; Sprinzl, M

    1994-01-01

    tRNA(Val) from Escherichia coli was aminoacylated with [1-13C]valine and its complex with Thermus thermophilus elongation factor EF-Tu.GTP was analyzed by 13C NMR spectroscopy. The results suggest that the aminoacyl residue of the valyl-tRNA in ternary complex with bacterial EF-Tu and GTP is not attached to tRNA by a regular ester bond to either a 2'- or 3'-hydroxyl group; instead, an intermediate orthoester acid structure with covalent linkage to both vicinal hydroxyls of the terminal adenosine-76 is formed. Mutation of arginine-59 located in the effector region of EF-Tu, a conserved residue in protein elongation factors and the alpha subunits of heterotrimeric guanine nucleotide-binding regulatory proteins (G proteins), abolishes the stabilization of the orthoester acid structure of aminoacyl-tRNA. PMID:8183898

  2. 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

    2013-04-01

    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.

  3. Measurement–model comparison of stabilized Criegee intermediate and highly oxygenated molecule production in the CLOUD chamber

    Directory of Open Access Journals (Sweden)

    N. Sarnela

    2018-02-01

    Full Text Available Atmospheric oxidation is an important phenomenon which produces large quantities of low-volatility compounds such as sulfuric acid and oxidized organic compounds. Such species may be involved in the nucleation of particles and enhance their subsequent growth to reach the size of cloud condensation nuclei (CCN. In this study, we investigate α-pinene, the most abundant monoterpene globally, and its oxidation products formed through ozonolysis in the Cosmic Leaving OUtdoor Droplets (CLOUD chamber at CERN (the European Organization for Nuclear Research. By scavenging hydroxyl radicals (OH with hydrogen (H2, we were able to investigate the formation of highly oxygenated molecules (HOMs purely driven by ozonolysis and study the oxidation of sulfur dioxide (SO2 driven by stabilized Criegee intermediates (sCIs. We measured the concentrations of HOM and sulfuric acid with a chemical ionization atmospheric-pressure interface time-of-flight (CI-APi-TOF mass spectrometer and compared the measured concentrations with simulated concentrations calculated with a kinetic model. We found molar yields in the range of 3.5–6.5 % for HOM formation and 22–32 % for the formation of stabilized Criegee intermediates by fitting our model to the measured sulfuric acid concentrations. The simulated time evolution of the ozonolysis products was in good agreement with measured concentrations except that in some of the experiments sulfuric acid formation was faster than simulated. In those experiments the simulated and measured concentrations met when the concentration reached a plateau but the plateau was reached 20–50 min later in the simulations. The results shown here are consistent with the recently published yields for HOM formation from different laboratory experiments. Together with the sCI yields, these results help us to understand atmospheric oxidation processes better and make the reaction parameters more comprehensive for broader use.

  4. Investigation of the oxygen exchange mechanism on Pt|yttria stabilized zirconia at intermediate temperatures: Surface path versus bulk path.

    Science.gov (United States)

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

    2011-11-30

    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.

  5. Investigation of the oxygen exchange mechanism on Pt|yttria stabilized zirconia at intermediate temperatures: Surface path versus bulk path

    International Nuclear Information System (INIS)

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

    2011-01-01

    Highlights: → Oxygen exchange kinetics of Pt on YSZ investigated by means of Pt model electrodes. → Two different geometry dependencies of the polarization resistance identified. → At higher temperatures the oxygen exchange reaction proceeds via a Pt surface path. → At lower temperatures a bulk path through the Pt thin film electrode is discussed. - Abstract: 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 deg. 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 deg. 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.

  6. Intermediate treatments

    Science.gov (United States)

    John R. Jones; Wayne D. Shepperd

    1985-01-01

    Intermediate treatments are those applied after a new stand is successfully established and before the final harvest. These include not only intermediate cuttings - primarily thinning - but also fertilization, irrigation, and protection of the stand from damaging agents.

  7. The H2A-H2B dimeric kinetic intermediate is stabilized by widespread hydrophobic burial with few fully native interactions.

    Science.gov (United States)

    Guyett, Paul J; Gloss, Lisa M

    2012-01-20

    The H2A-H2B histone heterodimer folds via monomeric and dimeric kinetic intermediates. Within ∼5 ms, the H2A and H2B polypeptides associate in a nearly diffusion limited reaction to form a dimeric ensemble, denoted I₂ and I₂*, the latter being a subpopulation characterized by a higher content of nonnative structure (NNS). The I₂ ensemble folds to the native heterodimer, N₂, through an observable, first-order kinetic phase. To determine the regions of structure in the I₂ ensemble, we characterized 26 Ala mutants of buried hydrophobic residues, spanning the three helices of the canonical histone folds of H2A and H2B and the H2B C-terminal helix. All but one targeted residue contributed significantly to the stability of I₂, the transition state and N₂; however, only residues in the hydrophobic core of the dimer interface perturbed the I₂* population. Destabilization of I₂* correlated with slower folding rates, implying that NNS is not a kinetic trap but rather accelerates folding. The pattern of Φ values indicated that residues forming intramolecular interactions in the peripheral helices contributed similar stability to I₂ and N₂, but residues involved in intermolecular interactions in the hydrophobic core are only partially folded in I₂. These findings suggest a dimerize-then-rearrange model. Residues throughout the histone fold contribute to the stability of I₂, but after the rapid dimerization reaction, the hydrophobic core of the dimer interface has few fully native interactions. In the transition state leading to N₂, more native-like interactions are developed and nonnative interactions are rearranged. Copyright © 2011 Elsevier Ltd. All rights reserved.

  8. Modulation of the Conformational Dynamics of Apo-Adenylate Kinase through a π-Cation Interaction.

    Science.gov (United States)

    Halder, Ritaban; Manna, Rabindra Nath; Chakraborty, Sandipan; Jana, Biman

    2017-06-15

    Large-scale conformational transition from open to closed state of adenylate kinase (ADK) is essential for its catalytic cycle. Apo-ADK undergoes conformational transition in a way that closely resembles an open-to-closed conformational transition. Here, equilibrium simulations, free-energy simulations, and quantum mechanics/molecular mechanics (QM/MM) calculations in combination with several bioinformatics approaches have been used to explore the molecular origin of this conformational transition in apo-ADK. In addition to its conventional open state, Escherichia coli apo-ADK adopts conformations that resemble a closed-like intermediate, the "half-open-half-closed" (HOHC) state, and a π-cation interaction can account for the stability of this HOHC state. Energetics and the electronic properties of this π-cation interaction have been explored using QM/MM calculations. Upon rescinding the π-cation interaction, the conformational landscape of the apo-ADK changes completely. The apo-ADK population is shifted completely toward the open state. This π-cation interaction is highly conserved in bacterial ADK; the cationic guanidinium moiety of a conserved ARG interacts with the delocalized π-electron cloud of either PHE or TYR. Interestingly, this study demonstrates the modulation of a principal protein dynamics by a conserved specific π-cation interaction across different organisms.

  9. The titanium tris-anilide cation [Ti(N[(t)Bu]Ar)3](+) stabilized as its perfluoro-tetra-phenylborate salt: structural characterization and synthesis in connection with redox activity of 4,4'-bipyridine dititanium complexes.

    Science.gov (United States)

    Spinney, Heather A; Clough, Christopher R; Cummins, Christopher C

    2015-04-21

    This work explores the reduction of 4,4'-bipyridine using two equivalents of the titanium(iii) complex Ti(N[(t)Bu]Ar)3 resulting in formation of a black, crystalline complex, (4,4'-bipy){Ti(N[(t)Bu]Ar)3}2, for which an X-ray structure determination is reported. The neutral, black, 4,4'-bipyridine-bridged bimetallic was found to be redox active, with mono- and di-anions being accessible electrochemically, and with the mono- and di-cations also being accessible chemically, and isolable, at least when using the weakly coordinating anion [B(C6F5)4](-) as the counter-ion. It proved possible to crystallize the salt [(4,4'-bipy){Ti(N[(t)Bu]Ar)3}2][B(C6F5)4]2 for a single-crystal X-ray structure investigation; in this instance it was revealed that the aromaticity of the 4,4'-bipyridine ligand, that had been disrupted upon reduction, had been regained. A rare cationic d(0) metal tris-amide complex, shown by X-ray crystallography to contain an intriguing pyramidal TiN3 core geometry, namely {Ti(N[(t)Bu]Ar)3}(+), could also be isolated when using [B(C6F5)4] as the essentially non-interacting counter-ion. This highly reactive cation should be considered as a potential intermediate in the plethora of reactions wherein Ti(N[(t)Bu]Ar)3 has been shown to effect the reduction of substrates including halogenated organic molecules, carbonyl compounds, organic nitriles, and metal complexes.

  10. Electrostatically driven resonance energy transfer in ?cationic? biocompatible indium phosphide quantum dots? ?Electronic supplementary information (ESI) available: Detailed experimental methods, the synthesis and characterization of QDs, bioimaging, stability studies, control experiments, and the calculation of various parameters involved in the resonance energy transfer process etc. See DOI: 10.1039/c7sc00592j Click here for additional data file.

    OpenAIRE

    Devatha, Gayathri; Roy, Soumendu; Rao, Anish; Mallick, Abhik; Basu, Sudipta; Pillai, Pramod P.

    2017-01-01

    Indium Phosphide Quantum Dots (InP QDs) have emerged as an alternative to toxic metal ion based QDs in nanobiotechnology. The ability to generate cationic surface charge, without compromising stability and biocompatibility, is essential in realizing the full potential of InP QDs in biological applications. We have addressed this challenge by developing a place exchange protocol for the preparation of cationic InP/ZnS QDs. The quaternary ammonium group provides the much required permanent posi...

  11. Structural and energetic study of cation-π-cation interactions in proteins.

    Science.gov (United States)

    Pinheiro, Silvana; Soteras, Ignacio; Gelpí, Josep Lluis; Dehez, François; Chipot, Christophe; Luque, F Javier; Curutchet, Carles

    2017-04-12

    Cation-π interactions of aromatic rings and positively charged groups are among the most important interactions in structural biology. The role and energetic characteristics of these interactions are well established. However, the occurrence of cation-π-cation interactions is an unexpected motif, which raises intriguing questions about its functional role in proteins. We present a statistical analysis of the occurrence, composition and geometrical preferences of cation-π-cation interactions identified in a set of non-redundant protein structures taken from the Protein Data Bank. Our results demonstrate that this structural motif is observed at a small, albeit non-negligible frequency in proteins, and suggest a preference to establish cation-π-cation motifs with Trp, followed by Tyr and Phe. Furthermore, we have found that cation-π-cation interactions tend to be highly conserved, which supports their structural or functional role. Finally, we have performed an energetic analysis of a representative subset of cation-π-cation complexes combining quantum-chemical and continuum solvation calculations. Our results point out that the protein environment can strongly screen the cation-cation repulsion, leading to an attractive interaction in 64% of the complexes analyzed. Together with the high degree of conservation observed, these results suggest a potential stabilizing role in the protein fold, as demonstrated recently for a miniature protein (Craven et al., J. Am. Chem. Soc. 2016, 138, 1543). From a computational point of view, the significant contribution of non-additive three-body terms challenges the suitability of standard additive force fields for describing cation-π-cation motifs in molecular simulations.

  12. Exploring backbone-cation alkyl spacers for multi-cation side chain anion exchange membranes

    Science.gov (United States)

    Zhu, Liang; Yu, Xuedi; Hickner, Michael A.

    2018-01-01

    In order to systematically study how the arrangement of cations on the side chain and length of alkyl spacers between cations impact the performance of multi-cation AEMs for alkaline fuel cells, a series of polyphenylene oxide (PPO)-based AEMs with different cationic side chains were synthesized. This work resulted in samples with two or three cations in a side chain pendant to the PPO backbone. More importantly, the length of the spacer between cations varied from 3 methylene (-CH2-) (C3) groups to 8 methylene (C8) groups. The highest conductivity, up to 99 mS/cm in liquid water at room temperature, was observed for the triple-cation side chain AEM with pentyl (C5) or hexyl (C6) spacers. The multi-cation AEMs were found to have decreased water uptake and ionic conductivity when the spacer chains between cations were lengthened from pentyl (C5) or hexyl (C6) to octyl (C8) linking groups. The triple-cation membranes with pentyl (C5) or hexyl (C6) groups between cations showed greatest stability after immersion in 1 M NaOH at 80 °C for 500 h.

  13. Strategies to increase the stability of intermediate moisture foods towards Zygosaccharomyces rouxii: The effect of temperature, ethanol, pH and water activity, with or without the influence of organic acids

    DEFF Research Database (Denmark)

    Vermeulen, A.; Nielsen, Cecilie Lykke Marvig; Daelman, J.

    2015-01-01

    Intermediate moisture foods (IMF) are in general microbiologically stable products. However, due to health concerns consumer demands are increasingly forcing producers to lower the fat, sugar and preservatives content, which impede the stability of the IMF products. One of the strategies to count......Intermediate moisture foods (IMF) are in general microbiologically stable products. However, due to health concerns consumer demands are increasingly forcing producers to lower the fat, sugar and preservatives content, which impede the stability of the IMF products. One of the strategies......, acetic acid had only an additive effect to ethanol and aw at low pH, whereas sorbic acid had also an additive effect at the higher pH values. For incubation periods longer than 30 days the growth/no growth boundary remained stable but enlarged gradually between day 60 and 90, except for the lower...

  14. Substrate-Triggered Formation and Remarkable Stability of the C-H-Cleaving Chloroferryl Intermediate in the Aliphatic Halogenase, SyrB2†

    Science.gov (United States)

    Matthews, Megan L.; Krest, Courtney M.; Barr, Eric W.; Vaillancourt, Frédéric H.; Walsh, Christopher T.; Green, Michael T.; Krebs, Carsten; Bollinger, J. Martin

    2009-01-01

    Aliphatic halogenases activate O2, cleave α-ketoglutarate (αKG) to CO2 and succinate, and form haloferryl [X-Fe(IV)=O; X = Cl, Br] complexes that cleave aliphatic C-H bonds to install halogens during the biosynthesis of natural products by non-ribosomal peptide synthetases (NRPSs). For the related αKG-dependent dioxygenases, it has been shown that reaction of the Fe(II) cofactor with O2 to form the C-H-cleaving ferryl complex is “triggered” by binding of the target substrate. In this study, we have tested for and defined structural determinants of substrate triggering (ST) in the halogenase, SyrB2, from the syringomycin E biosynthetic NRPS of Pseudomonas syringae B301D. As for other halogen ases, the substrate of SyrB2 is complex, consisting of l-Thr tethered via thioester linkage to a covalently bound phosphopantetheine (PPant) cofactor of a carrier protein, SyrB1. Without an appended amino acid, SyrB1 does not trigger formation of the chloroferryl intermediate state in SyrB2, even in the presence of free l-Thr or its analogues, but SyrB1 charged either by l-Thr or by any of several non-native amino acids does trigger the reaction by as much as 8,000-fold (for l-Thr-S-SyrB1). Triggering efficacy is sensitive to the structures of both the amino acid and the carrier protein, being diminished by 5–20-fold when the native l-Thr is replaced by another amino acid and by ∼ 40-fold when SyrB1 is replaced by a heterologous carrier protein, CytC2. The directing effect of the carrier protein and consequent tolerance for profound modifications to the target amino acid allow the chloroferryl state to be formed in the presence of substrates that perturb the ratio of its two putative coordination isomers, lack the target C-H bond (l-Ala-S-SyrB1), or contain a C-H bond of enhanced strength (l-cyclopropylglycyl-S-SyrB1). For the latter two cases, the SyrB2 chloroferryl state so formed exhibits unprecedented stability (t1/2 = 30 – 110 min at 0 °C), can be trapped in

  15. Intermediate Fragment

    DEFF Research Database (Denmark)

    Kruse Aagaard, Anders

    2015-01-01

    This text and its connected exhibition are aiming to reflect both on the thoughts, the processes and the outcome of the design and production of the artefact ‘Intermediate Fragment’ and making as a contemporary architectural tool in general. Intermediate Fragment was made for the exhibition ‘Enga...... of realising an exhibition object was conceived, but expanded, refined and concretised through this process. The context of the work shown here is an interest in a tighter, deeper connection between experimentally obtained material knowledge and architectural design....

  16. Test procedure for cation exchange chromatography

    International Nuclear Information System (INIS)

    Cooper, T.D.

    1994-01-01

    The purpose of this test plan is to demonstrate the synthesis of inorganic antimonate ion exchangers and compare their performance against the standard organic cation exchangers. Of particular interest is the degradation rate of both inorganic and organic cation exchangers. This degradation rate will be tracked by determining the ion exchange capacity and thermal stability as a function of time, radiation dose, and chemical reaction

  17. Luminescence and thermal stability tuning in (Ba,Mn)3(Gd,Y)Na(PO4)5F:Eu2+ phosphors via cation-substitution

    Science.gov (United States)

    Mei, Juan; Lv, Lemin; Gao, Junsong; Wei, Yi; Feng, Yuxin; Yan, Chunjie; Li, Guogang

    2018-04-01

    In this work, [Y3+-Gd3+] and [Mn2+-Ba2+] substitutions were designed in Ba3GdNa(PO4)5F:Eu2+ system, which were marked as BG1-xYxNPF:Eu2+ and B1-yMyGNPF:Eu2+, respectively. It is found that their luminescence properties and thermal stability could be obviously tuned. For BG1-xYxNPF:Eu2+ series, under 365 nm UV light, the emission spectra exhibited a continuous red-shift from 458 nm (x = 0) to 485 nm (x = 1) with the corresponding luminescence varying from blue light to cyan light. For B1-yMyGNPF:Eu2+ series, it was observed the coexistence of blue-green and enhanced red emission of Eu2+ and the appearance of Eu3+ emission when Mn2+ partly substituted Ba2+, resulting in a final white emission. In addition, the thermal stabilities of B1-yMyGNPF:Eu2+ were obviously improved with Mn2+ doping. The corresponding luminescence and thermal stability tuning mechanisms were investigated.

  18. [Noncovalent cation-π interactions--their role in nature].

    Science.gov (United States)

    Fink, Krzysztof; Boratyński, Janusz

    2014-11-07

    Non-covalent interactions play an extremely important role in organisms. The main non-covalent interactions in nature are: ion-ion interactions, dipole-dipole interactions, hydrogen bonds, and van der Waals interactions. A new kind of intermolecular interactions--cation-π interactions--is gaining increasing attention. These interactions occur between a cation and a π system. The main contributors to cation-π interactions are electrostatic, polarization and, to a lesser extent, dispersion interactions. At first, cation-π interactions were studied in a gas phase, with metal cation-aromatic system complexes. The characteristics of these complexes are as follows: an increase of cation atomic number leads to a decrease of interaction energy, and an increase of cation charge leads to an increase of interaction energy. Aromatic amino acids bind with metal cations mainly through interactions with their main chain. Nevertheless, cation-π interaction with a hydrophobic side chain significantly enhances binding energy. In water solutions most cations preferentially interact with water molecules rather than aromatic systems. Cation-π interactions occur in environments with lower accessibility to a polar solvent. Cation-π interactions can have a stabilizing role on the secondary, tertiary and quaternary structure of proteins. These interactions play an important role in substrate or ligand binding sites in many proteins, which should be taken into consideration when the screening of effective inhibitors for these proteins is carried out. Cation-π interactions are abundant and play an important role in many biological processes.

  19. Stabilization

    Directory of Open Access Journals (Sweden)

    Muhammad H. Al-Malack

    2016-07-01

    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.

  20. Explaining Operational Instability of Amine Transaminases : Substrate-Induced Inactivation Mechanism and Influence of Quaternary Structure on Enzyme-Cofactor Intermediate Stability

    NARCIS (Netherlands)

    Borner, Tim; Ramisch, Sebastian; Reddem, Eswar R.; Bartsch, Sebastian; Vogel, Andreas; Thunnissen, Andy-Mark W. H.; Adlercreutz, Patrick; Grey, Carl

    The insufficient operational stability of amine transaminases (ATA) constitutes a limiting factor for high productivity in chiral amine synthesis. In this work, we investigated the operational stability of a tetrameric ATA with 92% sequence identity to a Pseudomonas sp. transaminase and compared it

  1. 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

    2007-12-15

    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)

  2. Intermediate uveitis

    Directory of Open Access Journals (Sweden)

    Babu B

    2010-01-01

    Full Text Available Intermediate uveitis (IU is described as inflammation in the anterior vitreous, ciliary body and the peripheral retina. In the Standardization of Uveitis Nomenclature (SUN working group′s international workshop for reporting clinical data the consensus reached was that the term IU should be used for that subset of uveitis where the vitreous is the major site of the inflammation and if there is an associated infection (for example, Lyme disease or systemic disease (for example, sarcoidosis. The diagnostic term pars planitis should be used only for that subset of IU where there is snow bank or snowball formation occurring in the absence of an associated infection or systemic disease (that is, "idiopathic". This article discusses the clinical features, etiology, pathogenesis, investigations and treatment of IU.

  3. Enhancement of YBCO thin film thermal stability under 1 ATM oxygen pressure by Intermediate Cu.sub.2./sub. O nanolayer

    Czech Academy of Sciences Publication Activity Database

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

    2010-01-01

    Roč. 114, č. 22 (2010), s. 7543-7547 ISSN 1520-6106 R&D Projects: GA MŠk(CZ) ME10069 Institutional research plan: CEZ:AV0Z10100520 Keywords : YBCO thin films * thermal stability * thin film growth orientation * temperature optical microscopy Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.603, year: 2010

  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)

    1994-01-15

    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. A theoretical study of complexes formed between cations and curved aromatic systems: electrostatics does not always control cation-π interaction.

    Science.gov (United States)

    Carrazana-García, Jorge A; Cabaleiro-Lago, Enrique M; Rodríguez-Otero, Jesús

    2017-04-19

    The present work studies the interaction of two extended curved π-systems (corannulene and sumanene) with various cations (sodium, potassium, ammonium, tetramethylammonium, guanidinium and imidazolium). Polyatomic cations are models of groups found in important biomolecules in which cation-π interaction plays a fundamental role. The results indicate an important size effect: with extended π systems and cations of the size of potassium and larger, dispersion is much more important than has been generally recognized for cation-π interactions. In most of the systems studied here, the stability of the cation-π complexes is the result of a balanced combination of electrostatic, induction and dispersion contributions. None of the systems studied here owes its stability to the electrostatic interaction more than 42%. Induction dominates stabilization in complexes with sodium, and in some of the potassium and ammonium complexes. In complexes with large cations and with flat cations dispersion is the major stabilizing contribution and can provide more than 50% of the stabilization energy. This implies that theoretical studies of the cation-π interaction involving large or even medium-size fragments require a level of calculation capable of properly modelling dispersion. The separation between the cation and the π system is another important factor to take into account, especially when the fragments of the cation-π complex are bound (for example, to a protein backbone) and cannot interact at the most favourable distance.

  6. The effect of Al intermediate layer on thermal resistance of EB-PVD yttria-stabilized zirconia coatings on titanium substrate

    Science.gov (United States)

    Panin, Alexey; Panin, Victor; Kazachenok, Marina; Shugurov, Artur; Sinyakova, Elena; Martynov, Sergey; Rusyaev, Andrey; Kasterov, Artur

    2017-12-01

    The yttria-stabilized zirconia coatings sprayed on titanium substrates by the electron beam physical vapor deposition were subjected to thermal annealing in air at 1000°C for 1, 30 and 60 min. The delamination and fracture of the coatings are studied by the scanning electron microscopy and X-ray diffraction. It is shown that a magnetron sputtered Al interlayer between the coating and the substrate considerably improves the thermal resistance of ceramic coatings.

  7. Cation Exchange Water Softeners

    Science.gov (United States)

    WaterSense released a notice of intent to develop a specification for cation exchange water softeners. The program has made the decision not to move forward with a spec at this time, but is making this information available.

  8. Validating the technological feasibility of yttria-stabilized zirconia-based semiconducting-ionic composite in intermediate-temperature solid oxide fuel cells

    Science.gov (United States)

    Cai, Yixiao; Wang, Baoyuan; Wang, Yi; Xia, Chen; Qiao, Jinli; van Aken, Peter A.; Zhu, Bin; Lund, Peter

    2018-04-01

    YSZ as the electrolyte of choice has dominated the progressive development of solid oxide fuel cell (SOFC) technologies for many years. To enable SOFCs operating at intermediate temperatures of 600 °C or below, major technical advances were built on a foundation of a thin-film YSZ electrolyte, NiO anode, and perovskite cathode, e.g. La0.6Sr0.4Co0.8Fe0.2O3-δ (LSCF). Inspired by functionalities in engineered heterostructure interfaces, the present work uses the components from state-of-the-art SOFCs, i.e, the anode NiO-YSZ and the cathode LSCF-YSZ, or the convergence of all three components, i.e., NiO-YSZ-LSCF, to fabricate semiconductor-ionic membranes (SIMs) and devices. A series of proof-of-concept fuel cell devices are designed by using each of the above SIMs sandwiched between two semiconducting Ni0.8Co0.15Al0.05LiO2-δ (NCAL) layers. We systematically compare these novel designs at 600 °C with two reference fuel cells: a commercial product of anode-supported YSZ electrolyte thin-film cell, and a lab-assembled fuel cell with a conventional configuration of NiO-YSZ (anode)/YSZ (electrolyte)/LSCF-YSZ (cathode). In comparison to the reference cells, the SIM device in a configuration of NCAL/NiO-YSZ-LSCF/NCAL reaches more than 3-fold enhancement of the maximum power output. By using spherical aberration-corrected transmission electron microscopy and spectroscopy approaches, this work offers insight into the mechanisms underlying SIM-associated SOFC performance enhancement.

  9. Comparative energies of Zn(II) cation localization as a function of the distance between two forming cation position aluminium ions in high-silica zeolites

    NARCIS (Netherlands)

    Kachurovskaya, N.A.; Zhidomirov, G.M.; van Santen, R.A.

    2004-01-01

    Periodical calcns. of Zn(II) metal cation stabilization in cationic positions with distantly placed aluminum ions has been performed for high-silica ferrierite. It was found that decrease of the stabilization energy at large distances between Al ions (more than 10 .ANG.) is about of 2 eV in

  10. Protonic Conductors for Intermediate Temperature Fuel Cell Electrolytes: Superprotonic CsH2PO4 Stabilization and in-Doped SnP2O7 Structure Study

    Science.gov (United States)

    Martinez Salinas, Heber Jair

    Proton conductor solid electrolytes CsH2PO4 and In-doped tin pyrophosphate have been investigated as candidates to fill a gap of suitable electrolytes for fuel cells at the intermediate temperature range due their unusually high conductivities between 200 and 300 °C. Unfortunately, in the case of CsH2PO4, complicated experimental conditions, like a humidified environment, or high pressure, are needed to preserve the sought high conducting phase. In the first stage of this work, X-ray diffraction on CsH2PO 4 samples performed in air, and under normal conditions of humidity and pressure, evidence of the cubic phase of CsH2PO4 was observed during short intervals of temperature and time, starting at 215 °C and disappearing completely at 265 °C into a dehydrated phase. An AC impedance spectroscopy experimental setup has been assembled and data has been successfully collected on undoped, and doped CsH2PO 4 samples to investigate the effects of chemical and environmental modifications. Measurements performed in the temperature range 200 - 260 °C, and using the frequency range 1 - 6 MHz, showed that the high conducting phase of undoped CsH2PO4 was present for a very short interval of temperature. Additionally, these measurements showed that nano-silica-doped CsH2PO4, and CsH2PO4 under a humidified environment achieve the highest values of conductivity, above 10-2 S cm-1 among the samples tested. In the second stage of this investigation, AC impedance spectroscopy measurements were successfully performed on CsH2PO4 samples in air, at temperatures from 200 - 260 °C, and in the frequency range 1 - 6 MHz, inside a hermetically sealed stainless-steel chamber, which was designed and assembled in-house. Results showed that the highly conducting phase of CsH2PO 4 was achieved at temperatures measured above 230 °C, reaching conductivity values up to 1.7 x10-2 S cm-1, and remaining stable for over 40 hours. Consequent X-ray diffraction analysis of such samples showed that a

  11. Identifi cation of Sectarianism

    Directory of Open Access Journals (Sweden)

    Martinovich Vladimir

    2016-03-01

    Full Text Available «New religious movements and society» is traditionally one of the most sophisticated topics in the area of new religions studies. Its problem field is so huge that up to now by far not all important research themes where even touched by scientists from all over the world. The problem of the process of the identification of sectarianism by diff erent societal institutions is one of such untouched themes that is taken as the main subject of this article. This process by itself is an inseparable part of the every societal deliberate reaction to the very existence of unconventional religiosity, its unstructured and mainly structured types. The focal point of the article is step-by-step analysis of the general structure elements of the process of the identification of sectarianism without any reference to the specific time and place of its flow. Special attention is paid to the analysis of the subjects of the identification of sectarianism, to the criteria for religious groups to be qualified as new religious movements, and to the specific features of the process of documents filtration. The causes of selective perception of sectarianism are disclosed. Some main consequences and unpredictable outcomes of the process of the identification of sectarianism are described.

  12. Stabilization of the second oxyanion intermediate by 1,4-dihydroxy-2-naphthoyl-coenzyme A synthase of the menaquinone pathway: spectroscopic evidence of the involvement of a conserved aspartic acid.

    Science.gov (United States)

    Chen, Minjiao; Jiang, Ming; Sun, Yueru; Guo, Zu-Feng; Guo, Zhihong

    2011-07-05

    1,4-Dihydroxy-2-naphthoyl-coenzyme A (DHNA-CoA) synthase, or MenB, catalyzes an intramolecular Claisen condensation involving two oxyanion intermediates in the biosynthetic pathway of menaquinone, an essential respiration electron transporter in many microorganisms. Here we report the finding that the DHNA-CoA product and its analogues bind and inhibit the synthase from Escherichia coli with significant ultraviolet--visible spectral changes, which are similar to the changes induced by deprotonation of the free inhibitors in a basic solution. Dissection of the structure--affinity relationships of the inhibitors identifies the hydroxyl groups at positions 1 (C1-OH) and 4 (C4-OH) of DHNA-CoA or their equivalents as the dominant and minor sites, respectively, for the enzyme--ligand interaction that polarizes or deprotonates the bound ligands to cause the observed spectral changes. In the meantime, spectroscopic studies with active site mutants indicate that C4-OH of the enzyme-bound DHNA-CoA interacts with conserved polar residues Arg-91, Tyr-97, and Tyr-258 likely through a hydrogen bonding network that also includes Ser-161. In addition, site-directed mutation of the conserved Asp-163 to alanine causes a complete loss of the ligand binding ability of the protein, suggesting that the Asp-163 side chain is most likely hydrogen-bonded to C1-OH of DHNA-CoA to provide the dominant polarizing effect. Moreover, this mutation also completely eliminates the enzyme activity, strongly supporting the possibility that the Asp-163 side chain provides a strong stabilizing hydrogen bond to the tetrahedral oxyanion, which takes a position similar to that of C1-OH of the enzyme-bound DHNA-CoA and is the second high-energy intermediate in the intracellular Claisen condensation reaction. Interestingly, both Arg-91 and Tyr-97 are located in a disordered loop forming part of the active site of all available DHNA-CoA synthase structures. Their involvement in the interaction with the small

  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.

    2006-12-01

    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. The chemistry of amine radical cations produced by visible light photoredox catalysis

    Directory of Open Access Journals (Sweden)

    Jie Hu

    2013-10-01

    Full Text Available Amine radical cations are highly useful reactive intermediates in amine synthesis. They have displayed several modes of reactivity leading to some highly sought-after synthetic intermediates including iminium ions, α-amino radicals, and distonic ions. One appealing method to access amine radical cations is through one-electron oxidation of the corresponding amines under visible light photoredox conditions. This approach and subsequent chemistries are emerging as a powerful tool in amine synthesis. This article reviews synthetic applications of amine radical cations produced by visible light photocatalysis.

  15. Cation exchange properties of zeolites in hyper alkaline aqueous media.

    Science.gov (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

    2015-02-03

    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.

  16. SAXS Study of Sterically Stabilized Lipid Nanocarriers Functionalized by DNA

    Science.gov (United States)

    Angelov, Borislav; Angelova, Angelina; Filippov, Sergey; Karlsson, Göran; Terrill, Nick; Lesieur, Sylviane; Štěpánek, Petr

    2012-03-01

    The structure of novel spontaneously self-assembled plasmid DNA/lipid complexes is investigated by means of synchrotron radiation small-angle X-ray scattering (SAXS) and Cryo-TEM imaging. Liquid crystalline (LC) hydrated lipid systems are prepared using the non-ionic lipids monoolein and DOPE-PEG2000 and the cationic amphiphile CTAB. The employed plasmid DNA (pDNA) is encoding for the human protein brain-derived neurotrophic factor (BDNF). A coexistence of nanoparticulate objects with different LC inner organizations is established. A transition from bicontinuous membrane sponges, cubosome intermediates and unilamelar liposomes to multilamellar vesicles, functionalized by pDNA, is favoured upon binding and compaction of pBDNF onto the cationic PEGylated lipid nanocarriers. The obtained sterically stabilized multicompartment nanoobjects, with confined supercoiled plasmid DNA (pBDNF), are important in the context of multicompartment lipid nanocarriers of interest for gene therapy of neurodegenerative diseases.

  17. SAXS Study of Sterically Stabilized Lipid Nanocarriers Functionalized by DNA

    International Nuclear Information System (INIS)

    Angelov, Borislav; Filippov, Sergey; Štepánek, Petr; Angelova, Angelina; Lesieur, Sylviane; Karlsson, Göran; Terrill, Nick

    2012-01-01

    The structure of novel spontaneously self-assembled plasmid DNA/lipid complexes is investigated by means of synchrotron radiation small-angle X-ray scattering (SAXS) and Cryo-TEM imaging. Liquid crystalline (LC) hydrated lipid systems are prepared using the non-ionic lipids monoolein and DOPE-PEG 2000 and the cationic amphiphile CTAB. The employed plasmid DNA (pDNA) is encoding for the human protein brain-derived neurotrophic factor (BDNF). A coexistence of nanoparticulate objects with different LC inner organizations is established. A transition from bicontinuous membrane sponges, cubosome intermediates and unilamelar liposomes to multilamellar vesicles, functionalized by pDNA, is favoured upon binding and compaction of pBDNF onto the cationic PEGylated lipid nanocarriers. The obtained sterically stabilized multicompartment nanoobjects, with confined supercoiled plasmid DNA (pBDNF), are important in the context of multicompartment lipid nanocarriers of interest for gene therapy of neurodegenerative diseases.

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

    DEFF Research Database (Denmark)

    Chen, H. B.; Larsen, Torben

    1995-01-01

    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 and...

  19. Stabilized superconductors

    International Nuclear Information System (INIS)

    Wong, J.

    1975-01-01

    The stable, high field, high current composite wire comprises multiple filaments in a depleted bronze matrix, each filament comprising a type II superconducting, beta-tungsten structure, intermetallic compound layer jacketing and metallurgically bonded to a stabilizing copper core, directly or via an intermediate layer of refractory metal

  20. PGMA-Based Cationic Nanoparticles with Polyhydric Iodine Units for Advanced Gene Vectors.

    Science.gov (United States)

    Sun, Yue; Hu, Hao; Yu, Bingran; Xu, Fu-Jian

    2016-11-16

    It is crucial for successful gene delivery to develop safe, effective, and multifunctional polycations. Iodine-based small molecules are widely used as contrast agents for CT imaging. Herein, a series of star-like poly(glycidyl methacrylate) (PGMA)-based cationic vectors (II-PGEA/II) with abundant flanking polyhydric iodine units are prepared for multifunctional gene delivery systems. The proposed II-PGEA/II star vector is composed of one iohexol intermediate (II) core and five ethanolamine (EA) and II-difunctionalized PGMA arms. The amphipathic II-PGEA/II vectors readily self-assemble into well-defined cationic nanoparticles, where massive hydroxyl groups can establish a hydration shell to stabilize the nanoparticles. The II introduction improves cell viabilities of polycations. Moreover, by controlling the suitable amount of introduced II units, the resultant II-PGEA/II nanoparticles can produce fairly good transfection performances in different cell lines. Particularly, the II-PGEA/II nanoparticles induce much better in vitro CT imaging abilities in tumor cells than iohexol (one commonly used commercial CT contrast agent). The present design of amphipathic PGMA-based nanoparticles with CT contrast agents would provide useful information for the development of new multifunctional gene delivery systems.

  1. Sorption by cation exchange

    International Nuclear Information System (INIS)

    Bradbury, M.H.; Baeyens, B.

    1994-04-01

    A procedure for introducing exchange into geochemical/surface complexation codes is described. Beginning with selectivity coefficients, K c , defined in terms of equivalent fractional ion occupancies, a general expression for the molar based exchange code input parameters, K ex , is derived. In natural systems the uptake of nuclides onto complex sorbents often occurs by more than one mechanism. The incorporation of cation exchange and surface complexation into a geochemical code therefore enables sorption by both mechanisms to be calculated simultaneously. The code and model concepts are tested against sets of experimental data from widely different sorption studies. A proposal is made to set up a data base of selectivity coefficients. Such a data base would form part of a more general one consisting of sorption mechanism specific parameters to be used in conjunction with geochemical/sorption codes to model and predict sorption. (author) 6 figs., 6 tabs., 26 refs

  2. Radical Addition to Iminium Ions and Cationic Heterocycles

    Directory of Open Access Journals (Sweden)

    Johannes Tauber

    2014-10-01

    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.

  3. Gold for the generation and control of fluxional barbaralyl cations.

    Science.gov (United States)

    McGonigal, Paul R; de León, Claudia; Wang, Yahui; Homs, Anna; Solorio-Alvarado, César R; Echavarren, Antonio M

    2012-12-21

    The frog prince with his two identities pales in comparison with the shape-shifting barbaralyl cation, which exists as a mixture of 181,400 degenerate forms. Gold-catalyzed cycloisomerizations of 7-alkynyl cyclohepta-1,3,5-trienes were found to proceed via fluxional barbaralyl intermediates. The evolution of the intermediates into 1- or 2-substituted indenes could be controlled by the choice of gold complex. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Intermediality and media change

    OpenAIRE

    2012-01-01

    This book is about intermediality as an approach to analysing and understanding media change. Intermediality and Media Change is critical of technological determinism that characterises 'new media discourse' about the ongoing digitalization, framed as a revolution and creating sharp contrasts between old and new media. Intermediality instead emphasises paying attention to continuities between media of all types and privileges a comparative perspective on technological changes in media over ti...

  5. Effect of Intermediate Hosts on Emerging Zoonoses.

    Science.gov (United States)

    Cui, Jing-An; Chen, Fangyuan; Fan, Shengjie

    2017-08-01

    Most emerging zoonotic pathogens originate from animals. They can directly infect humans through natural reservoirs or indirectly through intermediate hosts. As a bridge, an intermediate host plays different roles in the transmission of zoonotic pathogens. In this study, we present three types of pathogen transmission to evaluate the effect of intermediate hosts on emerging zoonotic diseases in human epidemics. These types are identified as follows: TYPE 1, pathogen transmission without an intermediate host for comparison; TYPE 2, pathogen transmission with an intermediate host as an amplifier; and TYPE 3, pathogen transmission with an intermediate host as a vessel for genetic variation. In addition, we established three mathematical models to elucidate the mechanisms underlying zoonotic disease transmission according to these three types. Stability analysis indicated that the existence of intermediate hosts increased the difficulty of controlling zoonotic diseases because of more difficult conditions to satisfy for the disease to die out. The human epidemic would die out under the following conditions: TYPE 1: [Formula: see text] and [Formula: see text]; TYPE 2: [Formula: see text], [Formula: see text], and [Formula: see text]; and TYPE 3: [Formula: see text], [Formula: see text], [Formula: see text], and [Formula: see text] Simulation with similar parameters demonstrated that intermediate hosts could change the peak time and number of infected humans during a human epidemic; intermediate hosts also exerted different effects on controlling the prevalence of a human epidemic with natural reservoirs in different periods, which is important in addressing problems in public health. Monitoring and controlling the number of natural reservoirs and intermediate hosts at the right time would successfully manage and prevent the prevalence of emerging zoonoses in humans.

  6. Simplifying biochemical models with intermediate species

    DEFF Research Database (Denmark)

    Feliu, Elisenda; Wiuf, Carsten

    2013-01-01

    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...... 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...

  7. Electrospray ionization tandem mass spectrometry of ammonium cationized polyethers.

    Science.gov (United States)

    Nasioudis, Andreas; Heeren, Ron M A; van Doormalen, Irene; de Wijs-Rot, Nicolette; van den Brink, Oscar F

    2011-05-01

    Quaternary ammonium salts (Quats) and amines are known to facilitate the MS analysis of high molar mass polyethers by forming low charge state adduct ions. The formation, stability, and behavior upon collision-induced dissociation (CID) of adduct ions of polyethers with a variety of Quats and amines were studied by electrospray ionization quadrupole time-of-flight, quadrupole ion trap, and linear ion trap tandem mass spectrometry (MS/MS). The linear ion trap instrument was part of an Orbitrap hybrid mass spectrometer that allowed accurate mass MS/MS measurements. The Quats and amines studied were of different degree of substitution, structure, and size. The stability of the adduct ions was related to the structure of the cation, especially the amine's degree of substitution. CID of singly/doubly charged primary and tertiary ammonium cationized polymers resulted in the neutral loss of the amine followed by fragmentation of the protonated product ions. The latter reveals information about the monomer unit, polymer sequence, and endgroup structure. In addition, the detection of product ions retaining the ammonium ion was observed. The predominant process in the CID of singly charged quaternary ammonium cationized polymers was cation detachment, whereas their doubly charged adduct ions provided the same information as the primary and tertiary ammonium cationized adduct ions. This study shows the potential of specific amines as tools for the structural elucidation of high molar mass polyethers. © American Society for Mass Spectrometry, 2011

  8. Cationic polymers and porous materials

    KAUST Repository

    Han, Yu

    2017-04-27

    According to one or more embodiments, cationic polymers may be produced which include one or more monomers containing cations. Such cationic polymers may be utilized as structure directing agents to form mesoporous zeolites. The mesoporous zeolites may include micropores as well as mesopores, and may have a surface area of greater than 350 m2/g and a pore volume of greater than 0.3 cm3/g. Also described are core/shell zeolites, where at least the shell portion includes a mesoporous zeolite material.

  9. Cationic polymers and porous materials

    KAUST Repository

    Han, Yu; Tian, Qiwei; Dong, Xinglong; Liu, Zhaohui; Basset, Jean-Marie; Saih, Youssef; Sun, Miao; Xu, Wei; Shaikh, Sohel

    2017-01-01

    According to one or more embodiments, cationic polymers may be produced which include one or more monomers containing cations. Such cationic polymers may be utilized as structure directing agents to form mesoporous zeolites. The mesoporous zeolites may include micropores as well as mesopores, and may have a surface area of greater than 350 m2/g and a pore volume of greater than 0.3 cm3/g. Also described are core/shell zeolites, where at least the shell portion includes a mesoporous zeolite material.

  10. The cation-π interaction.

    Science.gov (United States)

    Dougherty, Dennis A

    2013-04-16

    The chemistry community now recognizes the cation-π interaction as a major force for molecular recognition, joining the hydrophobic effect, the hydrogen bond, and the ion pair in determining macromolecular structure and drug-receptor interactions. This Account provides the author's perspective on the intellectual origins and fundamental nature of the cation-π interaction. Early studies on cyclophanes established that water-soluble, cationic molecules would forego aqueous solvation to enter a hydrophobic cavity if that cavity was lined with π systems. Important gas phase studies established the fundamental nature of the cation-π interaction. The strength of the cation-π interaction (Li(+) binds to benzene with 38 kcal/mol of binding energy; NH4(+) with 19 kcal/mol) distinguishes it from the weaker polar-π interactions observed in the benzene dimer or water-benzene complexes. In addition to the substantial intrinsic strength of the cation-π interaction in gas phase studies, the cation-π interaction remains energetically significant in aqueous media and under biological conditions. Many studies have shown that cation-π interactions can enhance binding energies by 2-5 kcal/mol, making them competitive with hydrogen bonds and ion pairs in drug-receptor and protein-protein interactions. As with other noncovalent interactions involving aromatic systems, the cation-π interaction includes a substantial electrostatic component. The six (four) C(δ-)-H(δ+) bond dipoles of a molecule like benzene (ethylene) combine to produce a region of negative electrostatic potential on the face of the π system. Simple electrostatics facilitate a natural attraction of cations to the surface. The trend for (gas phase) binding energies is Li(+) > Na(+) > K(+) > Rb(+): as the ion gets larger the charge is dispersed over a larger sphere and binding interactions weaken, a classical electrostatic effect. On other hand, polarizability does not define these interactions. Cyclohexane is

  11. π-Cation Interactions in Molecular Recognition: Perspectives on Pharmaceuticals and Pesticides.

    Science.gov (United States)

    Liang, Zhibin; Li, Qing X

    2018-04-04

    The π-cation interaction that differs from the cation-π interaction is a valuable concept in molecular design of pharmaceuticals and pesticides. In this Perspective we present an up-to-date review (from 1995 to 2017) on bioactive molecules involving π-cation interactions with the recognition site, and categorize into systems of inhibitor-enzyme, ligand-receptor, ligand-transporter, and hapten-antibody. The concept of π-cation interactions offers use of π systems in a small molecule to enhance the binding affinity, specificity, selectivity, lipophilicity, bioavailability, and metabolic stability, which are physiochemical features desired for drugs and pesticides.

  12. Synthetic cation-selective nanotube: permeant cations chaperoned by anions.

    Science.gov (United States)

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

    2011-01-28

    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.

  13. Simultaneous anionic and cationic redox

    Science.gov (United States)

    Jung, Sung-Kyun; Kang, Kisuk

    2017-12-01

    It is challenging to unlock anionic redox activity, accompanied by full utilization of available cationic redox process, to boost capacity of battery cathodes. Now, material design by tuning the metal-oxygen interaction is shown to be a promising solution.

  14. Cation exchange assisted binding-elution strategy for enzymatic synthesis of human milk oligosaccharides (HMOs).

    Science.gov (United States)

    Zhu, Hailiang; Wu, Zhigang; Gadi, Madhusudhan Reddy; Wang, Shuaishuai; Guo, Yuxi; Edmunds, Garrett; Guan, Wanyi; Fang, Junqiang

    2017-09-15

    A cation exchange assisted binding-elution (BE) strategy for enzymatic synthesis of human milk oligosaccharides (HMOs) was developed. An amino linker was used to provide the cation ion under acidic condition which can be readily bound to cation exchange resin and then eluted off by saturated ammonium bicarbonate. Ammonium bicarbonate in the collections was easily removed by vacuum evaporation. This strategy circumvented the incompatible issue between glycosyltransferases and solid support or large polymers, and no purification was needed for intermediate products. With current approach, polyLacNAc backbones of HMOs and fucosylated HMOs were synthesized smoothly. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. an intermediate moisture meat

    African Journals Online (AJOL)

    STORAGESEVER

    2008-07-04

    Jul 4, 2008 ... traditional SM muscle without compromising quality. ... technique is intermediate moisture food processing. ... Traditionally, most tsire suya producers use ..... quality of Chinese purebred and European X Chinese crossbred ...

  16. Bacterial intermediate filaments

    DEFF Research Database (Denmark)

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

    2009-01-01

    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...

  17. Mapping Intermediality in Performance

    NARCIS (Netherlands)

    2010-01-01

    Mapping Intermediality in Performance benadert het vraagstuk van intermedialiteit met betrekking tot performance (vooral theater) vanuit vijf verschillende invalshoeken: performativiteit en lichaam; tijd en ruimte; digitale cultuur en posthumanisme; netwerken; pedagogiek en praxis. In deze boeiende

  18. 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.

  19. Intermediate algebra & analytic geometry

    CERN Document Server

    Gondin, William R

    1967-01-01

    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

  20. Cation disorder in Ga1212.

    Science.gov (United States)

    Greenwood, K B; Ko, D; Vander Griend, D A; Sarjeant, G M; Milgram, J W; Garrity, E S; DeLoach, D I; Poeppelmeier, K R; Salvador, P A; Mason, T O

    2000-07-24

    Substitution of calcium for strontium in LnSr2-xCaxCu2GaO7 (Ln = La, Pr, Nd, Gd, Ho, Er, Tm, and Yb) materials at ambient pressure and 975 degrees C results in complete substitution of calcium for strontium in the lanthanum and praseodymium systems and partial substitution in the other lanthanide systems. The calcium saturation level depends on the size of the Ln cation, and in all cases, a decrease in the lattice parameters with calcium concentration was observed until a common, lower bound, average A-cation size is reached. Site occupancies from X-ray and neutron diffraction experiments for LnSr2-xCaxCu2GaO7 (x = 0 and x = 2) confirm that the A-cations distribute between the two blocking-layer sites and the active-layer site based on size. A quantitative link between cation distribution and relative site-specific cation enthalpy for calcium, strontium, and lanthanum within the gallate structure is derived. The cation distribution in other similar materials can potentially be modeled.

  1. Role of distonic dimer radical cations in the radiation-induced polymerisation of vinyl ethers

    International Nuclear Information System (INIS)

    Naumov, Sergej; Janovsky, Igor; Knolle, Wolfgang; Mehnert, Reiner

    2005-01-01

    The experimental low-temperature EPR results and the quantum chemical calculations suggest that dimer radical cations of cyclic and aliphatic vinyl ethers (VE) plays a key role in starting of radiation-induced polymerisation. The main species observed at high 2,3-dihydrofuran (DHF), 2,3-dihydropyran (DHP) and VE concentration is the dimer radical cation. In the case of cyclic VE the dimer radical cation transforms through H-abstraction from neutral molecule into a carbocation and radical, which could start both cationic and free-radical polymerisation. However, in the case of aliphatic VE no further reactive species, which could start polymerisation, were observed. This is caused (in agreement with experiment and quantum chemical calculations) by the very high stability of dimer radical cation and calculated endothermity of H-abstraction reaction by dimer radical cation from monomer

  2. Develop guidelines for the design of pillar systems for shallow and intermediate depth, tabular, hard rock mines and provide a methodology for assessing hangingwall stability and support requirements for the panels between pillars

    CSIR Research Space (South Africa)

    York, G

    1998-12-01

    Full Text Available The design of hard rock pillars, in shallow to intermediate depth hard rock mines, has been redefined as the determination of the pillar system load bearing capacity. This entails the ability to design each of the components of the pillar system...

  3. Liquid-solid extraction of cationic metals by cationic amphiphiles

    International Nuclear Information System (INIS)

    Muller, W.

    2010-01-01

    In the field of selective separation for recycling of spent nuclear fuel, liquid-liquid extraction processes are widely used (PUREX, DIAMEX..) in industrial scale. In order to guarantee a sustainable nuclear energy for the forthcoming generations, alternative reprocessing techniques are under development. One of them bases on the studies from Heckmann et al in the 80's and consists in selectively precipitating actinides from aqueous waste solutions by cationic surfactants (liquid-solid extraction). This technique has some interesting advantages over liquid-liquid extraction techniques, because several steps are omitted like stripping or solvent washing. Moreover, the amount of waste is decreased considerably, since no contaminated organic solvent is produced. In this thesis, we have carried out a physico-chemical study to understand the specific interactions between the metallic cations with the cationic surfactant. First, we have analysed the specific effect of the different counter-ions (Cl - , NO 3 - , C 2 O 4 2- ) and then the effect of alkaline cations on the structural properties of the surfactant aggregation in varying thermodynamical conditions. Finally, different multivalent cations (Cu 2+ , Zn 2+ , UO 2 2+ , Fe 3+ , Nd 3+ , Eu 3+ , Th 4+ ) were considered; we have concluded that depending on the anionic complex of these metals formed in acidic media, we can observe either an adsorption at the micellar interface or not. This adsorption has a large influence of the surfactant aggregation properties and determines the limits of the application in term of ionic strength, temperature and surfactant concentration. (author) [fr

  4. 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.

    1981-05-01

    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.

  5. Intermediate-energy nuclear chemistry workshop

    International Nuclear Information System (INIS)

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

    1981-05-01

    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

  6. [Therapy of intermediate uveitis].

    Science.gov (United States)

    Doycheva, D; Deuter, C; Zierhut, M

    2014-12-01

    Intermediate uveitis is a form of intraocular inflammation in which the vitreous body is the major site of inflammation. Intermediate uveitis is primarily treated medicinally and systemic corticosteroids are the mainstay of therapy. When recurrence of uveitis or side effects occur during corticosteroid therapy an immunosuppressive treatment is required. Cyclosporine A is the only immunosuppressive agent that is approved for therapy of uveitis in Germany; however, other immunosuppressive drugs have also been shown to be effective and well-tolerated in patients with intermediate uveitis. In severe therapy-refractory cases when conventional immunosuppressive therapy has failed, biologics can be used. In patients with unilateral uveitis or when the systemic therapy is contraindicated because of side effects, an intravitreal steroid treatment can be carried out. In certain cases a vitrectomy may be used.

  7. Mobile communication and intermediality

    DEFF Research Database (Denmark)

    Helles, Rasmus

    2013-01-01

    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......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...

  8. Money distribution with intermediation

    OpenAIRE

    Teles, Caio Augusto Colnago

    2013-01-01

    This pap er analyzes the distribution of money holdings in a commo dity money search-based mo del with intermediation. Intro ducing heterogeneity of costs to the Kiyotaki e Wright ( 1989 ) mo del, Cavalcanti e Puzzello ( 2010) gives rise to a non-degenerated distribution of money. We extend further this mo del intro ducing intermediation in the trading pro cess. We show that the distribution of money matters for savings decisions. This gives rises to a xed p oint problem for the ...

  9. Organic cation rhodamines for screening organic cation transporters in early stages of drug development.

    Science.gov (United States)

    Ugwu, Malachy C; Oli, Angus; Esimone, Charles O; Agu, Remigius U

    The aim of this study was to investigate the suitability of rhodamine-123, rhodamine-6G and rhodamine B as non-radioactive probes for characterizing organic cation transporters in respiratory cells. Fluorescent characteristics of the compounds were validated under standard in vitro drug transport conditions (buffers, pH, and light). Uptake/transport kinetics and intracellular accumulation of the compounds were investigated. Uptake/transport mechanisms were investigated by comparing the effect of pH, temperature, concentration, polarity, OCTs/OCTNs inhibitors/substrates, and metabolic inhibitors on the cationic dyes uptake in Calu-3 cells. Fluorescence stability and intensity of the compounds were altered by buffer composition, light, and pH. Uptake of the dyes was concentration-, temperature- and pH-dependent. OCTs/OCTNs inhibitors significantly reduced intracellular accumulation of the compounds. Whereas rhodamine-B uptake was sodium-dependent, pH had no effect on rhodamine-123 and rhodamine-6G uptake. Transport of the dyes across the cells was polarized: (AP→BL>BL→AP transport) and saturable: {V max =14.08±2.074, K m =1821±380.4 (rhodamine-B); V max =6.555±0.4106, K m =1353±130.4 (rhodamine-123) and V max =0.3056±0.01402, K m =702.9±60.97 (rhodamine-6G)}. The dyes were co-localized with MitoTracker®, the mitochondrial marker. Cationic rhodamines, especially rhodamine-B and rhodamine- 6G can be used as organic cation transporter substrates in respiratory cells. During such studies, buffer selection, pH and light exposure should be taken into consideration. Copyright © 2016 Elsevier Inc. All rights reserved.

  10. Cations form sequence selective motifs within DNA grooves via a combination of cation-pi and ion-dipole/hydrogen bond interactions.

    Science.gov (United States)

    Stewart, Mikaela; Dunlap, Tori; Dourlain, Elizabeth; Grant, Bryce; McFail-Isom, Lori

    2013-01-01

    The fine conformational subtleties of DNA structure modulate many fundamental cellular processes including gene activation/repression, cellular division, and DNA repair. Most of these cellular processes rely on the conformational heterogeneity of specific DNA sequences. Factors including those structural characteristics inherent in the particular base sequence as well as those induced through interaction with solvent components combine to produce fine DNA structural variation including helical flexibility and conformation. Cation-pi interactions between solvent cations or their first hydration shell waters and the faces of DNA bases form sequence selectively and contribute to DNA structural heterogeneity. In this paper, we detect and characterize the binding patterns found in cation-pi interactions between solvent cations and DNA bases in a set of high resolution x-ray crystal structures. Specifically, we found that monovalent cations (Tl⁺) and the polarized first hydration shell waters of divalent cations (Mg²⁺, Ca²⁺) form cation-pi interactions with DNA bases stabilizing unstacked conformations. When these cation-pi interactions are combined with electrostatic interactions a pattern of specific binding motifs is formed within the grooves.

  11. Interactions of nucleobases with alkali earth metal cations--electrospray ionization mass spectrometric study.

    Science.gov (United States)

    Frańska, Magdalena

    2007-01-01

    Interactions of nucleobases with alkali earth metal cations have been studied by electrospray ionization mass spectrometry (ESI-MS). Nucleobases containing at least one oxygen atom form stable complexes with alkali earth metal cations. This phenomenon can be explained on the grounds of the well known theory of hard and soft acids and bases. Uracil and thymine make complexes only when in their deprotonoted forms. The cations of great radii (Sr(2+), Ba(2+)) are more prone to form complexes of stoichiometry 1:1 with uracil and thymine than the cations of small radii (Mg(2+), Ca(2+)). On the other hand, Mg(2+) forms complexes of stoichiometry 2:1 and 3:2 with uracil and thymine. Gas-phase stabilities of the 1:1 complexes are higher for the cations of small radii, in contrast to the solution stabilities. For cytosine and 9- methylhypoxantine the 1:1 complexes of their deprotonated forms are observed at higher cone voltage as a result of HCl molecule loss from the complexes containing the counter ion (Cl(-)). In solution, more stable complexes are formed with metal cations of low radii. Gas-phase stability of the complexes formed by deprotonated 9- methyl-hypoxantine increases with increasing metal cation radius.

  12. Effect of reagents and medium nature on direction of cation-radical transformations in the reaction of diarylamines with nitrosonium borofluoride

    International Nuclear Information System (INIS)

    Koshechko, V.G.; Inozemtsev, A.N.; Pokhodenko, V.O.

    1983-01-01

    Diphenylamine and 4, 4'-dimethoxydiphenylamine in acetonitrile are oxidized monoelectronically by NOBF 4 . On the 4, 4'-dimethoxydiphenylamine example a maximum current concentration of intermediate cation-radicals formed in this reaction is measured. Cation-radicals in acetonitrile get dimeric transforming into products of oxidizing condensation of amines, with no respective nitrozamines being observed. Nitrosamines production on through cation-radical-NO recombination is realized but in the presence of protonoacceptor solvents, in particular pyridine

  13. Vibrational Spectroscopy of Cation and Anion Channelrhodopsins

    Science.gov (United States)

    Yi, Adrian S.

    Optogenetics is a technique to control and monitor cell activity with light by expression of specific microbial rhodopsins. Cation channelrhodopsins (CCRs) and anion channelrhodopsins (ACRs) have been demonstrated to activate and silence cell activity, respectively. In this dissertation, the molecular mechanisms of two channelrhodopsins are studied: a CCR from Chlamydomonas augustae (CaChR1) and an ACR from Guillardia theta (GtACR1). The recently discovered GtACR1is especially interesting, as it achieves neural silencing with 1/1000th of the light intensity compared to previous microbial rhodopsin silencing ion pumps. Static and time-resolved resonance Raman, FTIR difference, and UV-visible spectroscopies were utilized in addition to various biochemical and genetic techniques to explore the molecular mechanisms of these channelrhodopsins. In CaChR1, Glu169 and Asp299 residues are located nearby the Schiff base (SB) similar to the homologous residues Asp85 and Asp212, which exist in an ionized state in unphotolyzed bacteriorhodopsin (BR) and play a key role in proton pumping. We observe significant changes in the protonation states of the SB, Glu169, and Asp299 of CaChR1 leading up to the open-channel P2 state, where all three groups exist in a charge neutral state. This unusual charge neutrality along with the position of these groups in the CaChR1 ion channel suggests that charge neutrality plays an important role in cation gating and selectivity in these low efficiency CCRs. Significant differences exist in the photocycle and protonation/hydrogen bonding states of key residues inGtACR1compared to BR and CaChR1. Resonance Raman studies reveal that in the unphotolyzed state of GtACR1, residues Glu68, Ser97 (BR Asp85 homolog), and Asp234 (BR Asp212 homolog) located near the SB exist in charge neutral states. Furthermore, upon K formation, these residues do not change their protonation states. At room temperature, a slow decay of the red-shifted K intermediate is

  14. Cation binding to 15-TBA quadruplex DNA is a multiple-pathway cation-dependent process.

    Science.gov (United States)

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

    2011-12-01

    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. © The Author(s) 2011. Published by Oxford University Press.

  15. Cation binding to 15-TBA quadruplex DNA is a multiple-pathway cation-dependent process

    Science.gov (United States)

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

    2011-01-01

    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. PMID:21893589

  16. Thermodynamics and Cation Diffusion in the Oxygen Ion Conductor Lsgm

    Science.gov (United States)

    Martin, M.; Schulz, O.

    Perovskite type oxides based on LaGaO3 are of large technical interest because of their high oxygen-ion conductivity. Lanthanum gallate doped with Sr on A- and Mg on B-sites, La1-xSrxGa1-yMgyO3-(x+y)/2 (LSGM), reaches higher oxygen-ion conductivities than yttria-doped zirconia (YSZ). Thus LSGM represents a promising alternative for YSZ as electrolyte in solid oxide fuel cells (SOFC). Cells using thin LSGM-layers as electrolyte are expected to operate at intermediate temperatures around 700°C for more than 30000 hours without severe degradation. A potential long term degradation effect of LSGM is kinetic demixing of the electrolyte, caused by different cation diffusion coefficients. In this paper we report on experimental studies concerning the phase diagram of LSGM and the diffusion of cations. Cation self-diffusion of 139La, 84Sr and 25Mg and cation impurity diffusion of 144Nd, 89Y and 56Fe in polycrystalline LSGM samples was investigated by secondary ion mass spectrometry (SIMS) for temperatures between 900°C and 1400°C. It was found that diffusion occurs by means of bulk and grain boundaries. The bulk diffusion coefficients are similar for all cations with activation energies which are strongly dependent on temperature. At high temperatures, the activation energies are about 5 eV, while at low temperatures values of about 2 eV are found. These results are explained by a frozen in defect structure at low temperatures. This means that the observed activation energy at low temperatures represents only the migration energy of the different cations while the observed activation energy at high temperatures is the sum of the defect formation energy and the migration energy. The migration energies for all cations are nearly identical, although 139La, 84Sr and 144Nd are occupying A-sites while 25Mg and 56Fe are occupying B-sites in the perovskite-structure. To explain these experimental findings we propose a defect cluster containing cation vacancies in both the A

  17. Liquid-solid extraction of metallic cations by cationic amphiphiles

    International Nuclear Information System (INIS)

    Mueller, Wolfram; Sievers, Torsten K.; Zemb, Thomas; Diat, Olivier; Sievers, Torsten K.; Dejugnat, Christophe

    2012-01-01

    In the field of selective metal ion separation, liquid-liquid extraction is usually conducted through an emulsion mixing of hydrophobic complexants dispersed in an organic phase and acidic water containing the ionic species. Recently, it has been shown that amphiphilic complexants could influence strongly extraction efficiency by enhancing the interfacial interaction between the metal ion in the aqueous and the complexant in the organic phase. Moreover, these amphiphiles can also substitute the organic phase if an appropriate aliphatic chain is chosen. The dispersion of such amphiphilic complexants in an aqueous solution of salt mixtures is not only attractive for studying specific interactions but also to better the understanding of complex formation in aqueous solution of multivalent metal ions, such as lanthanides and actinides. This understanding is of potential interest for a broad range of industries including purification of rare earth metals and pollute treatment e.g. of fission byproducts. This principle can also be applied to liquid-solid extraction, where the final state of the separation is a solid phase containing the selectively extracted ions. Indeed, a novel solid-liquid extraction method exploits the selective precipitation of metal ions from an aqueous salt mixture using a cationic surfactant, below its Krafft point (temperature below which the long aliphatic chains of surfactant crystallize). This technique has been proven to be highly efficient for the separation of actinides and heavy metal using long chain ammonium or pyridinium amphiphiles. The most important point in this process is the recognition of cationic metal ions by cationic surfactants. By computing the free energy of the polar head group per micelle as a function of the different counter-anions, we have demonstrated for the first time that different interactions exist between the micellar surface and the ions. These interactions depend on the nature of the cation but also on

  18. Exploration of minima on the C7H surface: Structural, stability- and ...

    Indian Academy of Sciences (India)

    index for aromaticity could distinguish well between aromatic, non-aromatic and anti-aromatic ... 7 isomers; cation stability; cation geometry; charge distribution; NICS; hybridization state; ..... resonance hybrid or as the most important canoni-.

  19. Comparison of different cationized proteins as biomaterials for nanoparticle-based ocular gene delivery.

    Science.gov (United States)

    Zorzi, Giovanni K; Párraga, Jenny E; Seijo, Begoña; Sanchez, Alejandro

    2015-11-01

    Cationized polymers have been proposed as transfection agents for gene therapy. The present work aims to improve the understanding of the potential use of different cationized proteins (atelocollagen, albumin and gelatin) as nanoparticle components and to investigate the possibility of modulating the physicochemical properties of the resulting nanoparticle carriers by selecting specific protein characteristics in an attempt to improve current ocular gene-delivery approaches. The toxicity profiles, as well as internalization and transfection efficiency, of the developed nanoparticles can be modulated by modifying the molecular weight of the selected protein and the amine used for cationization. The most promising systems are nanoparticles based on intermediate molecular weight gelatin cationized with the endogenous amine spermine, which exhibit an adequate toxicological profile, as well as effective association and protection of pDNA or siRNA molecules, thereby resulting in higher transfection efficiency and gene silencing than the other studied formulations. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. 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.; Martinez Caicedo, D.A.; 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.; Orebi Gann, G.D.; 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.; St. John, J.M.; 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.

    2015-01-01

    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...

  1. The Intermediate Neutrino Program

    Energy Technology Data Exchange (ETDEWEB)

    Adams, C.; et al.

    2015-03-23

    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.

  2. The Intermediate Neutrino Program

    Energy Technology Data Exchange (ETDEWEB)

    Adams, C. [Yale Univ., New Haven, CT (United States); Alonso, J. R. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Ankowski, A. M. [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Asaadi, J. A. [Syracuse Univ., NY (United States); Ashenfelter, J. [Yale Univ., New Haven, CT (United States); Axani, S. N. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Babu, K [Oklahoma State Univ., Stillwater, OK (United States); Backhouse, C. [California Inst. of Technology (CalTech), Pasadena, CA (United States); Band, H. R. [Yale Univ., New Haven, CT (United States); Barbeau, P. S. [Duke Univ., Durham, NC (United States); Barros, N. [Univ. of Pennsylvania, Philadelphia, PA (United States); Bernstein, A. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Betancourt, M. [Illinois Inst. of Technology, Chicago, IL (United States); Bishai, M. [Brookhaven National Lab. (BNL), Upton, NY (United States); Blucher, E. [Univ. of Chicago, IL (United States); Bouffard, J. [State Univ. of New York (SUNY), Albany, NY (United States); Bowden, N. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Brice, S. [Illinois Inst. of Technology, Chicago, IL (United States); Bryan, C. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Camilleri, L. [Columbia Univ., New York, NY (United States); Cao, J. [Inst. of High Energy Physics, Beijing (China); Carlson, J. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Carr, R. E. [Columbia Univ., New York, NY (United States); Chatterjee, A. [Univ. of Texas, Arlington, TX (United States); Chen, M. [Univ. of California, Irvine, CA (United States); Chen, S. [Tsinghua Univ., Beijing (China); Chiu, M. [Brookhaven National Lab. (BNL), Upton, NY (United States); Church, E. D. [Illinois Inst. of Technology, Chicago, IL (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Collar, J. I. [Univ. of Chicago, IL (United States); Collin, G. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Conrad, J. M. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Convery, M. R. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Cooper, R. L. [Indiana Univ., Bloomington, IN (United States); Cowen, D. [Pennsylvania State Univ., University Park, PA (United States); Davoudiasl, H. [Brookhaven National Lab. (BNL), Upton, NY (United States); Gouvea, A. D. [Northwestern Univ., Evanston, IL (United States); Dean, D. J. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Deichert, G. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Descamps, F. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); DeYoung, T. [Michigan State Univ., East Lansing, MI (United States); Diwan, M. V. [Brookhaven National Lab. (BNL), Upton, NY (United States); Djurcic, Z. [Argonne National Lab. (ANL), Argonne, IL (United States); Dolinski, M. J. [Drexel Univ., Philadelphia, PA (United States); Dolph, J. [Brookhaven National Lab. (BNL), Upton, NY (United States); Donnelly, B. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Dwyer, D. A. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Dytman, S. [Univ. of Pittsburgh, PA (United States); Efremenko, Y. [Univ. of Tennessee, Knoxville, TN (United States); Everett, L. L. [Univ. of Wisconsin, Madison, WI (United States); Fava, A. [University of Padua, Padova (Italy); Figueroa-Feliciano, E. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Fleming, B. [Yale Univ., New Haven, CT (United States); Friedland, A. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Fujikawa, B. K. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Gaisser, T. K. [Univ. of Delaware, Newark, DE (United States); Galeazzi, M. [Univ. of Miami, FL (United States); Galehouse, DC [Univ. of Akron, OH (United States); Galindo-Uribarri, A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Garvey, G. T. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Gautam, S. [Tribhuvan Univ., Kirtipur (Nepal); Gilje, K. E. [Illinois Inst. of Technology, Chicago, IL (United States); Gonzalez-Garcia, M. [Stony Brook Univ., NY (United States); Goodman, M. C. [Argonne National Lab. (ANL), Argonne, IL (United States); Gordon, H. [Brookhaven National Lab. (BNL), Upton, NY (United States); Gramellini, E. [Yale Univ., New Haven, CT (United States); Green, M. P. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Guglielmi, A. [University of Padua, Padova (Italy); Hackenburg, R. W. [Brookhaven National Lab. (BNL), Upton, NY (United States); Hackenburg, A. [Yale Univ., New Haven, CT (United States); Halzen, F. [Univ. of Wisconsin, Madison, WI (United States); Han, K. [Yale Univ., New Haven, CT (United States); Hans, S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Harris, D. [Illinois Inst. of Technology, Chicago, IL (United States); Heeger, K. M. [Yale Univ., New Haven, CT (United States); Herman, M. [Brookhaven National Lab. (BNL), Upton, NY (United States); Hill, R. [Univ. of Chicago, IL (United States); Holin, A. [Univ. College London, Bloomsbury (United Kingdom); Huber, P. [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Jaffe, D. E. [Brookhaven National Lab. (BNL), Upton, NY (United States); Johnson, R. A. [Univ. of Cincinnati, OH (United States); Joshi, J. [Brookhaven National Lab. (BNL), Upton, NY (United States); Karagiorgi, G. [Univ. of Manchester (United Kingdom); Kaufman, L. J. [Indiana Univ., Bloomington, IN (United States); Kayser, B. [Illinois Inst. of Technology, Chicago, IL (United States); Kettell, S. H. [Brookhaven National Lab. (BNL), Upton, NY (United States); Kirby, B. J. [Brookhaven National Lab. (BNL), Upton, NY (United States); Klein, J. R. [Univ. of Texas, Arlington, TX (United States); Kolomensky, Y. G. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Kriske, R. M. [Univ. of Minnesota, Minneapolis, MN (United States); Lane, C. E. [Drexel Univ., Philadelphia, PA (United States); Langford, T. J. [Yale Univ., New Haven, CT (United States); Lankford, A. [Univ. of California, Irvine, CA (United States); Lau, K. [Univ. of Houston, TX (United States); Learned, J. G. [Univ. of Hawaii, Honolulu, HI (United States); Ling, J. [Univ. of Illinois, Urbana-Champaign, IL (United States); Link, J. M. [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Lissauer, D. [Brookhaven National Lab. (BNL), Upton, NY (United States); Littenberg, L. [Brookhaven National Lab. (BNL), Upton, NY (United States); Littlejohn, B. R. [Illinois Inst. of Technology, Chicago, IL (United States); Lockwitz, S. [Illinois Inst. of Technology, Chicago, IL (United States); Lokajicek, M. [Inst. of Physics of the Academy of Sciences of Czech Republic, Prague (Czech Republic); Louis, W. C. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Luk, K. [Univ. of California, Berkeley, CA (United States); Lykken, J. [Illinois Inst. of Technology, Chicago, IL (United States); Marciano, W. J. [Brookhaven National Lab. (BNL), Upton, NY (United States); Maricic, J. [Univ. of Hawaii, Honolulu, HI (United States); Markoff, D. M. [North Carolina Central Univ., Durham, NC (United States); Caicedo, D. A. M. [Illinois Inst. of Technology, Chicago, IL (United States); Mauger, C. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Mavrokoridis, K. [Univ. of Liverpool (United Kingdom); McCluskey, E. [Illinois Inst. of Technology, Chicago, IL (United States); McKeen, D. [Univ. of Washington, Seattle, WA (United States); McKeown, R. [Thomas Jefferson National Accelerator Facility (TJNAF), Newport News, VA (United States); Mills, G. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Mocioiu, I. [Pennsylvania State Univ., University Park, PA (United States); Monreal, B. [Univ. of California, Santa Barbara, CA (United States); Mooney, M. R. [Brookhaven National Lab. (BNL), Upton, NY (United States); Morfin, J. G. [Illinois Inst. of Technology, Chicago, IL (United States); Mumm, P. [National Inst. of Standards and Technology (NIST), Boulder, CO (United States); Napolitano, J. [Temple Univ., Philadelphia, PA (United States); Neilson, R. [Drexel Univ., Philadelphia, PA (United States); Nelson, J. K. [College of William and Mary, Williamsburg, VA (United States); Nessi, M. [European Organization for Nuclear Research (CERN), Geneva (Switzerland); Norcini, D. [Yale Univ., New Haven, CT (United States); Nova, F. [Univ. of Texas, Austin, TX (United States); Nygren, D. R. [Univ. of Texas, Arlington, TX (United States); Gann, GDO [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Palamara, O. [Illinois Inst. of Technology, Chicago, IL (United States); Parsa, Z. [Brookhaven National Lab. (BNL), Upton, NY (United States); Patterson, R. [California Inst. of Technology (CalTech), Pasadena, CA (United States); Paul, P. [Stony Brook Univ., NY (United States); Pocar, A. [Univ. of Massachusetts, Amherst, MA (United States); Qian, X. [Brookhaven National Lab. (BNL), Upton, NY (United States); Raaf, J. L. [Illinois Inst. of Technology, Chicago, IL (United States); Rameika, R. [Illinois Inst. of Technology, Chicago, IL (United States); Ranucci, G. [National Inst. of Nuclear Physics, Milano (Italy); Ray, H. [Univ. of Florida, Gainesville, FL (United States); Reyna, D. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Rich, G. C. [Triangle Universities Nuclear Lab., Durham, NC (United States); Rodrigues, P. [Univ. of Rochester, NY (United States); Romero, E. R. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States); Rosero, R. [Brookhaven National Lab. (BNL), Upton, NY (United States); Rountree, S. D. [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Rybolt, B. [Univ. of Tennessee, Knoxville, TN (United States); Sanchez, M. C. [Iowa State Univ., Ames, IA (United States); Santucci, G. [Stony Brook Univ., NY (United States); Schmitz, D. [Univ. of Chicago, IL (United States); Scholberg, K. [Duke Univ., Durham, NC (United States); Seckel, D. [Univ. of Delaware, Newark, DE (United States); Shaevitz, M. [Columbia Univ., New York, NY (United States); Shrock, R. [Stony Brook Univ., NY (United States); Smy, M. B. [Univ. of California, Irvine, CA (United States); Soderberg, M. [Syracuse Univ., NY (United States); Sonzogni, A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Sousa, A. B. [Univ. of Cincinnati, OH (United States); Spitz, J. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); John, J. M. S. [Univ. of Cincinnati, OH (United States); Stewart, J. [Brookhaven National Lab. (BNL), Upton, NY (United States); Strait, J. B. [Illinois Inst. of Technology, Chicago, IL (United States); Sullivan, G. [Univ. of Maryland, College Park, MD (United States); Svoboda, R. [Univ. of California, Davis, CA (United States); Szelc, A. M. [Yale Univ., New Haven, CT (United States); Tayloe, R. [Indiana Univ., Bloomington, IN (United States); Thomson, M. A. [Univ. of Cambridge (United Kingdom); Toups, M. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Vacheret, A. [Univ. of Oxford (United Kingdom); Vagins, M. [Univ. of California, Irvine, CA (United States); Water, R. G. V. D. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Vogelaar, R. B. [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Weber, M. [Bern (Switzerland); Weng, W. [Brookhaven National Lab. (BNL), Upton, NY (United States); Wetstein, M. [Univ. of Chicago, IL (United States); White, C. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); White, B. R. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Whitehead, L. [Univ. of Houston, TX (United States); Whittington, D. W. [Indiana Univ., Bloomington, IN (United States); Wilking, M. J. [Stony Brook Univ., NY (United States); Wilson, R. J. [Colorado State Univ., Fort Collins, CO (United States); Wilson, P. [Illinois Inst. of Technology, Chicago, IL (United States); Winklehner, D. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Winn, D. R. [Fairfield Univ., CT (United States); Worcester, E. [Brookhaven National Lab. (BNL), Upton, NY (United States); Yang, L. [Univ. of Illinois, Urbana-Champaign, IL (United States); Yeh, M [Brookhaven National Lab. (BNL), Upton, NY (United States); Yokley, Z. W. [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Yoo, J. [Illinois Inst. of Technology, Chicago, IL (United States); Yu, B. [Brookhaven National Lab. (BNL), Upton, NY (United States); Yu, J. [Univ. of Texas, Arlington, TX (United States); Zhang, C. [Brookhaven National Lab. (BNL), Upton, NY (United States)

    2017-04-03

    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.

  3. Intermediate energy data

    International Nuclear Information System (INIS)

    Koning, A.J.; Fukahori, T.; Hasegawa, A.

    1998-01-01

    Subgroup 13 (SG13) on Intermediate Energy Nuclear data was formed by NEA Nuclear Science Committee to solve common problems of these types of data for nuclear applications. An overview is presented in this final report of the present activities of SG13, including data needs, high-priority nuclear data request list (nuclides), compilation of experimental data, specialists meetings and benchmarks, data formats and data libraries. Some important accomplishments are summarized, and recommendations are presented. (R.P.)

  4. Tripodal receptors for cation and anion sensors

    NARCIS (Netherlands)

    Kuswandi, Bambang; Nuriman, [Unknown; Verboom, Willem; Reinhoudt, David

    2006-01-01

    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

  5. Separation of alkali, alkaline earth and rare earth cations by liquid membranes containing macrocyclic carriers. Third progress report, September 1, 1980-April 1, 1981

    International Nuclear Information System (INIS)

    Christensen, J.J.

    1981-01-01

    The overall objective of this project is to study the use of liquid membrane systems employing macrocyclic ligand carriers in making separations among metal cations. During the third year of the project, work continued in the development of a mathematical model to describe cation transport. The model was originally developed to describe the relationship between cation transport rate (J/sub M/) and the cation-macrocycle stability constant (K). The model was tested by determining the rates of transport of alkali and alkaline earth cations through chloroform membranes containing carrier ligands where the stability constants for their reaction with cations in methanol were known. From the results, it is clear that the model correctly describes the dependence of J/sub M/ on log K. The model also correctly describes the effect of cation concentration and carrier concentration on cation transport rates, as detailed in the previous progress report. During the third year of the project, the transport model was expanded so as to apply to competitive transport of cations from mixtures of two cations in the source aqueous phase. Data were collected under these conditions and the ability of the model to predict the flux of each cation was tested. Representative data of this type are presented along with corresponding data which were obtained when each cation was transported by the same carrier from a source phase containing only that cation. Comparison of transport rates determined under the two experimental conditions indicates that the relationship between the two sets of data is complex. To date, a few of these data involving transport from binary cation mixtures have been tested against the transport model. It was found that the model correctly predicts the cation fluxes from cation mixtures. These preliminary results indicate that the transport model can successfully predict separation factors when cation mixtures are used

  6. Heavy metal cations permeate the TRPV6 epithelial cation channel.

    Science.gov (United States)

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

    2011-01-01

    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. Copyright © 2010 Elsevier Ltd. All rights reserved.

  7. Isoporphyrin Intermediate in Heme Oxygenase Catalysis

    Science.gov (United States)

    Evans, John P.; Niemevz, Fernando; Buldain, Graciela; de Montellano, Paul Ortiz

    2008-01-01

    Human heme oxygenase-1 (hHO-1) catalyzes the O2- and NADPH-dependent oxidation of heme to biliverdin, CO, and free iron. The first step involves regiospecific insertion of an oxygen atom at the α-meso carbon by a ferric hydroperoxide and is predicted to proceed via an isoporphyrin π-cation intermediate. Here we report spectroscopic detection of a transient intermediate during oxidation by hHO-1 of α-meso-phenylheme-IX, α-meso-(p-methylphenyl)-mesoheme-III, and α-meso-(p-trifluoromethylphenyl)-mesoheme-III. In agreement with previous experiments (Wang, J., Niemevz, F., Lad, L., Huang, L., Alvarez, D. E., Buldain, G., Poulos, T. L., and Ortiz de Montellano, P. R. (2004) J. Biol. Chem. 279, 42593–42604), only the α-biliverdin isomer is produced with concomitant formation of the corresponding benzoic acid. The transient intermediate observed in the NADPH-P450 reductase-catalyzed reaction accumulated when the reaction was supported by H2O2 and exhibited the absorption maxima at 435 and 930 nm characteristic of an isoporphyrin. Product analysis by reversed phase high performance liquid chromatography and liquid chromatography electrospray ionization mass spectrometry of the product generated with H2O2 identified it as an isoporphyrin that, on quenching, decayed to benzoylbiliverdin. In the presence of H218O2, one labeled oxygen atom was incorporated into these products. The hHO-1-isoporphyrin complexes were found to have half-lives of 1.7 and 2.4 h for the p-trifluoromethyl- and p-methyl-substituted phenylhemes, respectively. The addition of NADPH-P450 reductase to the H2O2-generated hHO-1-isoporphyrin complex produced α-biliverdin, confirming its role as a reaction intermediate. Identification of an isoporphyrin intermediate in the catalytic sequence of hHO-1, the first such intermediate observed in hemoprotein catalysis, completes our understanding of the critical first step of heme oxidation. PMID:18487208

  8. Cationic electrodepositable coating composition comprising lignin

    Science.gov (United States)

    Fenn, David; Bowman, Mark P; Zawacky, Steven R; Van Buskirk, Ellor J; Kamarchik, Peter

    2013-07-30

    A cationic electrodepositable coating composition is disclosed. The present invention in directed to a cationic electrodepositable coating composition comprising a lignin-containing cationic salt resin, that comprises (A) the reaction product of: lignin, an amine, and a carbonyl compound; (B) the reaction product of lignin, epichlorohydrin, and an amine; or (C) combinations thereof.

  9. Au70S20(PPh3)12: an intermediate sized metalloid gold cluster stabilized by the Au4S4 ring motif and Au-PPh3 groups.

    Science.gov (United States)

    Kenzler, Sebastian; Schrenk, Claudio; Frojd, Andrew R; Häkkinen, Hannu; Clayborne, Andre Z; Schnepf, Andreas

    2018-01-02

    Reducing (Ph 3 P)AuSC(SiMe 3 ) 3 with l-Selectride® gives the medium-sized metalloid gold cluster Au 70 S 20 (PPh 3 ) 12 . Computational studies show that the phosphine bound Au-atoms not only stabilize the electronic structure of Au 70 S 20 (PPh 3 ) 12 , but also behave as electron acceptors leading to auride-like gold atoms on the exterior.

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

    International Nuclear Information System (INIS)

    Messina, S.; Juan, A.; Larrondo, S.; Irigoyen, B.; Amadeo, N.

    2008-01-01

    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 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 4 phase the Sb and V cations defects stabilize the V in a higher oxidation state (V 4+ ). Calculations of the adsorption energy for different toluene adsorption geometries on the VSbO 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 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 4+ ) are the species, which preferentially incorporate lattice oxygen to the reduced Sb cations. Thus, the cation defects would stabilize the V 4+ species in the VSbO 4 structure, determining its ability to provide lattice oxygen as a reactant

  11. Prediction of Intrinsic Cesium Desorption from Na-Smectite in Mixed Cation Solutions.

    Science.gov (United States)

    Fukushi, Keisuke; Fukiage, Tomo

    2015-09-01

    Quantitative understanding of the stability of sorbed radionuclides in smectite is necessary to assess the performance of engineering barriers used for nuclear waste disposal. Our previous study demonstrated that the spatial organization of the smectite platelets triggered by the divalent cations led to the apparent fixation of intrinsic Cs in smectite, because some Cs is retained inside the formed tactoids. Natural water is usually a mixture of Na(+) and divalent cations (Ca(2+) and Mg(2+)). This study therefore investigated the desorption behavior of intrinsic Cs in Na-smecite in mixed Na(+)-divalent cation solutions under widely various cation concentrations using batch experiments, grain size measurements, and cation exchange modeling (CEM). Results show that increased Na(+) concentrations facilitate Cs desorption because Na(+) serves as the dispersion agent. A linear relation was obtained between the logarithm of the Na(+) fraction and the accessible Cs fraction in smectite. That relation enables the prediction of accessible Cs fraction as a function of solution cationic compositions. The corrected CEM considering the effects of the spatial organization suggests that the stability of intrinsic Cs in the smectite is governed by the Na(+) concentration, and suggests that it is almost independent of the concentrations of divalent cations in natural water.

  12. Electrostatically driven resonance energy transfer in "cationic" biocompatible indium phosphide quantum dots.

    Science.gov (United States)

    Devatha, Gayathri; Roy, Soumendu; Rao, Anish; Mallick, Abhik; Basu, Sudipta; Pillai, Pramod P

    2017-05-01

    Indium Phosphide Quantum Dots (InP QDs) have emerged as an alternative to toxic metal ion based QDs in nanobiotechnology. The ability to generate cationic surface charge, without compromising stability and biocompatibility, is essential in realizing the full potential of InP QDs in biological applications. We have addressed this challenge by developing a place exchange protocol for the preparation of cationic InP/ZnS QDs. The quaternary ammonium group provides the much required permanent positive charge and stability to InP/ZnS QDs in biofluids. The two important properties of QDs, namely bioimaging and light induced resonance energy transfer, are successfully demonstrated in cationic InP/ZnS QDs. The low cytotoxicity and stable photoluminescence of cationic InP/ZnS QDs inside cells make them ideal candidates as optical probes for cellular imaging. An efficient resonance energy transfer ( E ∼ 60%) is observed, under physiological conditions, between the cationic InP/ZnS QD donor and anionic dye acceptor. A large bimolecular quenching constant along with a linear Stern-Volmer plot confirms the formation of a strong ground state complex between the cationic InP/ZnS QDs and the anionic dye. Control experiments prove the role of electrostatic attraction in driving the light induced interactions, which can rightfully form the basis for future nano-bio studies between cationic InP/ZnS QDs and anionic biomolecules.

  13. Asymmetric cation-binding catalysis

    DEFF Research Database (Denmark)

    Oliveira, Maria Teresa; Lee, Jiwoong

    2017-01-01

    The employment of metal salts is quite limited in asymmetric catalysis, although it would provide an additional arsenal of safe and inexpensive reagents to create molecular functions with high optical purity. Cation chelation by polyethers increases the salts' solubility in conventional organic...... 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...... highly enantioselective silylation reactions in polyether-generated chiral environments, and leading to a record-high turnover in asymmetric organocatalysis. This can lead to further applications by the asymmetric use of other inorganic salts in various organic transformations....

  14. The intermediate state in Patd

    African Journals Online (AJOL)

    ) Jesus had assumed. (concerning the 'intermediate state') as existing, anything which does not exist. Three basic things about the intermediate state emerge from the parable: (a) Jesus recognizes that at the moment of death, in ipso articulo.

  15. Anaerobic toxicity of cationic silver nanoparticles

    International Nuclear Information System (INIS)

    Gitipour, Alireza; Thiel, Stephen W.; Scheckel, Kirk G.; Tolaymat, Thabet

    2016-01-01

    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 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"−"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"−"1 as silver), only the cationic BPEI-AgNPs demonstrated toxicity similar in magnitude to that of Ag"+. Both citrate and PVP-AgNPs did not exhibit toxicity at the 100 mg L"−"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"−"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.

  16. Electrodeposition properties of modified cational epoxy resin-type photoresist

    International Nuclear Information System (INIS)

    Yong He; Yunlong Zhang; Feipeng Wu; Miaozhen Li; Erjian Wang

    1999-01-01

    Multi-component cationic epoxy and acrylic resin system for ED photoresist was used in this work, since they can provide better storage stability for ED emulsion and better physical and chemical properties of deposited film than one-component system. The cationic main resin (AE) was prepared from amine modified epoxy resins and then treated with acetic acid. The amination degree was controlled as required. The synthetic procedure of cationic main resins is described in scheme I. The ED photoresist (AME) is composed of cationic main resin (AE) and nonionic multifunctional acrylic crosslinkers (PETA), in combination with suitable photo-initiator. They can easily be dispersed in deionized water to form a stable ED emulsion. The exposed part of deposited film upon UV irradiation occurs crosslinking to produce an insoluble semi-penetrating network and the unexposed part remains good solubility in the acidic water solution. It is readily utilized for fabrication of fine micropattern. The electrodeposition are carried out on Cu plate at room temperature. To evaluate the electrodeposition properties of ED photoresist (AME), the different influences are examined

  17. [Intermediate energy nuclear physics

    International Nuclear Information System (INIS)

    1989-01-01

    This report summarizes work in experimental Intermediate Energy Nuclear Physics carried out between October 1, 1988 and October 1, 1989 at the Nuclear Physics Laboratory of the University of Colorado, Boulder, under grant DE-FG02-86ER-40269 with the United States Department of Energy. The experimental program is very broadly based, including pion-nucleon studies at TRIUMF, inelastic pion scattering and charge exchange reactions at LAMPF, and nucleon charge exchange at LAMPF/WNR. In addition, a number of other topics related to accelerator physics are described in this report

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

    KAUST Repository

    Dey, Raju

    2016-04-13

    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.

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

    KAUST Repository

    Dey, Raju; Samantaray, Manoja; Callens, Emmanuel; Hamieh, Ali Imad Ali; Emwas, Abdul-Hamid M.; Abou-Hamad, Edy; Kavitake, Santosh Giridhar; Basset, Jean-Marie

    2016-01-01

    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. Radiation-induced polymerisation of 2,3-dihydrofuran: free-radical or cationic mechanism?

    International Nuclear Information System (INIS)

    Janovsky, Igor; Naumov, Sergej; Knolle, Wolfgang; Mehnert, Reiner

    2005-01-01

    Concentrated (10 mol%) solutions of 2,3-dihydrofuran in CFCl 2 CF 2 Cl matrix were irradiated at 77 K and several intermediates (dimer radical cation, dihydrofuryl radical, and polymer radicals) were observed by low-temperature EPR spectroscopy. The irradiated solutions yielded after melting a polymeric product, which was characterised by IR spectroscopy and gel permeation chromatography. The polydisperse polymer is assumed to be formed mainly by a cationic process initiated by a dimer carbocation. The free-radical mechanism via the dihydrofuryl radical leads to low molecular weight oligomers only. Quantum chemical calculations support the interpretation of the experimental results

  1. Base Stability of Aminocyclopropeniums

    Science.gov (United States)

    2017-11-01

    PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) US Army Research Laboratory Weapons and Materials Research Directorate (ATTN: RDRL-WMM-G) 2800 Powder...Mill Road Adelphi, MD 20783-1138 8. PERFORMING ORGANIZATION REPORT NUMBER ARL-TR-8204 9. SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES...fuel cells to test their utility in anion exchange membranes. While the aminocyclopropeniums showed poor base stability, the cyclopropenium cation

  2. Cation-Coupled Bicarbonate Transporters

    OpenAIRE

    Aalkjaer, Christian; Boedtkjer, Ebbe; Choi, Inyeong; Lee, Soojung

    2014-01-01

    Cation-coupled HCO3− transport was initially identified in the mid-1970s when pioneering studies showed that acid extrusion from cells is stimulated by CO2/HCO3− and associated with Na+ and Cl− movement. The first Na+-coupled bicarbonate transporter (NCBT) was expression-cloned in the late 1990s. There are currently five mammalian NCBTs in the SLC4-family: the electrogenic Na,HCO3-cotransporters NBCe1 and NBCe2 (SLC4A4 and SLC4A5 gene products); the electroneutral Na,HCO3-cotransporter NBCn1 ...

  3. Cation disorder in shocked orthopyroxene.

    Science.gov (United States)

    Dundon, R. W.; Hafner, S. S.

    1971-01-01

    The study of cation distributions over nonequivalent lattice sites in minerals may reveal information on the history of temperature and pressure in rocks. Chemically homogeneous orthopyroxene specimens were shocked under well-controlled conditions in the laboratory in order to provide a basis for the interpretation of more complex natural materials. As a result of the investigation it is concluded that the distribution of magnesium and iron over the M1 and M2 positions in Bamle enstatite shocked at 1 megabar is highly disordered. It corresponds to an equilibrium distribution of at least 1000 C.

  4. Cation coordination in oxychloride glasses

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, J A [Energy Technology Division, Argonne National Laboratory, Argonne, IL (United States); Holland, D [Physics Department, Warwick University, Coventry (United Kingdom); Bland, J [Physics Department, University of Liverpool, PO Box 147, Liverpool (United Kingdom); Johnson, C E [Physics Department, Northern Illinois University, DeKalb, IL (United States); Thomas, M F [Physics Department, University of Liverpool, PO Box 147, Liverpool (United Kingdom)

    2003-02-19

    Glasses containing mixtures of cations and anions of nominal compositions [Sb{sub 2}O{sub 3}]{sub x} - [ZnCl{sub 2}]{sub 1-x} where x = 0.25, 0.50, 0.75, and 1.00, have been studied by means of neutron diffraction and Raman and Moessbauer spectroscopy. There is preferential bonding within the system with the absence of Sb-Cl bonds. Antimony is found to be threefold coordinated to oxygen, and zinc fourfold coordinated. The main contributing species are of the form [Sb(OSb){sub 2}(OZn)] and [Zn(ClZn){sub 2}(OSb){sub 2}].

  5. Cation coordination in oxychloride glasses

    International Nuclear Information System (INIS)

    Johnson, J A; Holland, D; Bland, J; Johnson, C E; Thomas, M F

    2003-01-01

    Glasses containing mixtures of cations and anions of nominal compositions [Sb 2 O 3 ] x - [ZnCl 2 ] 1-x where x = 0.25, 0.50, 0.75, and 1.00, have been studied by means of neutron diffraction and Raman and Moessbauer spectroscopy. There is preferential bonding within the system with the absence of Sb-Cl bonds. Antimony is found to be threefold coordinated to oxygen, and zinc fourfold coordinated. The main contributing species are of the form [Sb(OSb) 2 (OZn)] and [Zn(ClZn) 2 (OSb) 2

  6. Measurement of antioxidant activity with trifluoperazine dihydrochloride radical cation

    Directory of Open Access Journals (Sweden)

    M.N. Asghar

    2008-06-01

    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.

  7. Intermediate products of radiolytic conversions of 6-aminophenalenone in ethanol

    International Nuclear Information System (INIS)

    Semenova, G.V.; Ponomarev, A.V.; Kartasheva, L.I.; Pikaev, A.K.

    1992-01-01

    Intermediate products of the conversions of 6-aminophenalenone in ethanol were investigated by pulse radiolysis. In alkaline medium the main product is the 6-aminophenalenone radical cation, the optical absorption spectrum of which contains two bands with maxima at 355 and 400 nm. The precursors of this particle are e s , CH 3 CHOH and CH 3 CHO - radicals. In neutral and acid medium, radical cations are protonated in reactions with alcohol and hydrogen ions. The H-adduct of 6-aminophenalenone that arises has optical absorption maxima at 350 and 390 nm. The presence of two maxima is due to two different structures of the product. The molar extinction coefficients of the radical anions and H-adducts of 6-aminophenalenone and the rate constants of the reactions involving them were estimated. 6 refs., 4 figs., 2 tabs

  8. Thermal stability of BaSrO thin films and the influence of Al intermediate layers to the electrical properties of high-k Si(001)/BaSrO/Au MOS diodes

    Energy Technology Data Exchange (ETDEWEB)

    Islam, Shariful; Mueller-Sajak, Dirk; Pfnuer, Herbert [Leibniz-Universitaet Hannover, Inst. f. Festkoerperphysik (Germany); Cosceev, Alexander; Hofmann, Karl R. [Leibniz-Universitaet Hannover, Bauelemente der Mikro- und Nanoelektronik (Germany)

    2011-07-01

    MOS diodes with crystalline Ba{sub 0.7}Sr{sub 0.3}O gate oxide and Au gate metal on n- and p-Si(001) were produced, which have a dielectric constant of {epsilon}{sub r}{approx}28. The oxides were grown on structured Si(001) in a UHV chamber by MBE in oxygen ambient conditions and capped with 100nm Au for ex-situ electrical measurements. I-V measurements show low leakage currents compared to SiO{sub 2} with the same EOT. From C-V measurements we extracted with the Terman method a density of interface states, D{sub it}, of only {approx}10{sup 10}eV{sup -1}cm{sup -2}. We tested the thermal stability of these oxides and investigated them with X-Ray Photoelectron Spectroscopy (XPS). They are fully stable up to 450 C but convert to other chemical species, most likely silicates, at higher temperatures. But even at 700 C no formation of SiO{sub 2} at the interface to Si was detectable. To improve the adhesion between the Au gate metal and the oxide we evaporated a thin layer of Al at the Au/oxide interface. This causes a thickness dependent shift of the flatband voltage. We present our XPS measurements of the chemical origin of this shift.

  9. ADSORPTION METHOD FOR SEPARATING METAL CATIONS

    Science.gov (United States)

    Khym, J.X.

    1959-03-10

    The chromatographic separation of fission product cations is discussed. By use of this method a mixture of metal cations containing Zr, Cb, Ce, Y, Ba, and Sr may be separated from one another. Mentioned as preferred exchange adsorbents are resins containing free sulfonic acid groups. Various eluants, such as tartaric acid, HCl, and citric acid, used at various acidities, are employed to effect the selective elution and separation of the various fission product cations.

  10. Electronic spectra of astrophysically interesting cations

    Energy Technology Data Exchange (ETDEWEB)

    Maier, John P., E-mail: j.p.maier@unibas.ch; Rice, Corey A., E-mail: j.p.maier@unibas.ch; Mazzotti, Fabio J., E-mail: j.p.maier@unibas.ch; Johnson, Anatoly, E-mail: j.p.maier@unibas.ch [Department of Chemistry, University of Basel, Klingelbergstr. 80, CH-4056 Basel (Switzerland)

    2015-01-22

    The electronic spectra of polyacetylene cations were recorded at 20K in the laboratory in an ion trap instrument. These can then be compared with diffuse interstellar band (DIB) absorptions. Examination of recently published data shows that the attribution of a weak DIB at ∼506.9 nm to diacetylene cation is not justified. Study of the higher excited electronic states of polyacetylene cations shows that their widths can still be sufficiently narrow for consideration as DIB carriers.

  11. Discourses and Models of Intermediality

    OpenAIRE

    Schröter, Jens

    2011-01-01

    In his article "Discourses and Models of Intermediality" Jens Schröter discusses the question as to what relations do different discourses pose between different "media." Schröter identifies four models of discourse: 1) synthetic intermediality: a "fusion" of different media to super-media, a model with roots in the Wagnerian concept of Gesamtkunstwerk with political connotations, 2) formal (or transmedial) intermediality: a concept based on formal structures not "specific" to one medium but ...

  12. Information acquisition and financial intermediation

    OpenAIRE

    Boyarchenko, Nina

    2012-01-01

    This paper considers the problem of information acquisition in an intermediated market, where the specialists have access to superior technology for acquiring information. These informational advantages of specialists relative to households lead to disagreement between the two groups, changing the shape of the intermediation-constrained region of the economy and increasing the frequency of periods when the intermediation constraint binds. Acquiring the additional information is, however, cost...

  13. Uranium isotope separation using styrene cation exchangers

    International Nuclear Information System (INIS)

    Kahovec, J.

    1980-01-01

    The separation of 235 U and 238 U isotopes is carried out either by simple isotope exchange in the system uranium-cation exchanger (sulphonated styrene divinylbenzene resin), or by combination of isotope exchange in a uranium-cation exchanger (Dowex 50, Amberlite IR-120) system and a chemical reaction. A review is presented of elution agents used, the degree of cation exchanger cross-linking, columns length, and 235 U enrichment. The results are described of the isotope effect study in a U(IV)-U(VI)-cation exchanger system conducted by Japanese and Romanian authors (isotope exchange kinetics, frontal analysis, reverse (indirect) frontal analysis). (H.S.)

  14. Cation-π interactions in structural biology

    OpenAIRE

    Gallivan, Justin P.; Dougherty, Dennis A.

    1999-01-01

    Cation-pi interactions in protein structures are identified and evaluated by using an energy-based criterion for selecting significant sidechain pairs. Cation-pi interactions are found to be common among structures in the Protein Data Bank, and it is clearly demonstrated that, when a cationic sidechain (Lys or Arg) is near an aromatic sidechain (Phe, Tyr, or Trp), the geometry is biased toward one that would experience a favorable cation-pi interaction. The sidechain of Arg is more likely tha...

  15. Simultaneous anion and cation mobility in polypyrrole

    DEFF Research Database (Denmark)

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

    2003-01-01

    and the expulsion of anions; a broad anodic peak centered at ca. - 0.5 V representing the expulsion of cations; and a second broad peak at +0.2 to +0.5 V corresponding to anions being inserted. Although the motion of cations is the most important, as expected, there is a significant anion contribution, thereby...... 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...

  16. Isotope substitution effects on preferred conformations of some hydrocarbon radical cations

    International Nuclear Information System (INIS)

    Lunell, S.; Eriksson, L.A.

    1992-01-01

    The stability of different conformational isomers of partially deuterated radical cations of ethane, butane, and cyclopropane is studied at the HF/6-31G** and MP2/6-31G** levels. It is shown that the superposition patterns of spectra corresponding to different isomers, observed in ESR spectroscopy, are accurately reproduced by Boltzmann statistics based on differences in vibrational zero-point energies (ZPE), provided that the temperature is high enough to overcome existing barriers toward internal pseudorotation in the cations. For the ethane and butane cations, the most stable conformations are, as expected, those which are deuterated in the short CH bonds, while this is found not to be the case for the cyclopropane cation. The latter result is explained by shifts in the low-frequency bending modes, which counteract the anticipated isotope effect on the C H stretching modes

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

    Energy Technology Data Exchange (ETDEWEB)

    Jia, Hanzhong, E-mail: jiahz@ms.xjb.ac.cn [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: cywang@ms.xjb.ac.cn [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)

    2015-04-28

    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.

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

    International Nuclear Information System (INIS)

    Jia, Hanzhong; Li, Li; Chen, Hongxia; Zhao, Yue; Li, Xiyou; Wang, Chuanyi

    2015-01-01

    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 3+ > Al 3+ > Cu 2+ >> Ca 2+ > K + > Na + , 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 + -smectite and K + -smectite surface favors solar light absorption, resulting in enhanced direct photodecomposition of PAHs. On the other hand, smectite clays saturated with Fe 3+ , Al 3+ , and Cu 2+ are highly photoreactive and can act as potential catalysts giving rise to oxidative radicals such as O 2 − · , 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

  19. Solvation Effect on Complexation of Alkali Metal Cations by a Calix[4]arene Ketone Derivative.

    Science.gov (United States)

    Požar, Josip; Nikšić-Franjić, Ivana; Cvetnić, Marija; Leko, Katarina; Cindro, Nikola; Pičuljan, Katarina; Borilović, Ivana; Frkanec, Leo; Tomišić, Vladislav

    2017-09-14

    The medium effect on the complexation of alkali metal cations with a calix[4]arene ketone derivative (L) was systematically examined in methanol, ethanol, N-methylformamide, N,N-dimethylformamide, dimethyl sulfoxide, and acetonitrile. In all solvents the binding of Na + cation by L was rather efficient, whereas the complexation of other alkali metal cations was observed only in methanol and acetonitrile. Complexation reactions were enthalpically controlled, while ligand dissolution was endothermic in all cases. A notable influence of the solvent on NaL + complex stability could be mainly attributed to the differences in complexation entropies. The higher NaL + stability in comparison to complexes with other alkali metal cations in acetonitrile was predominantly due to a more favorable complexation enthalpy. The 1 H NMR investigations revealed a relatively low affinity of the calixarene sodium complex for inclusion of the solvent molecule in the calixarene hydrophobic cavity, with the exception of acetonitrile. Differences in complex stabilities in the explored solvents, apart from N,N-dimethylformamide and acetonitrile, could be mostly explained by taking into account solely the cation and complex solvation. A considerable solvent effect on the complexation equilibria was proven to be due to an interesting interplay between the transfer enthalpies and entropies of the reactants and the complexes formed.

  20. The MHD intermediate shock interaction with an intermediate wave: Are intermediate shocks physical?

    International Nuclear Information System (INIS)

    Wu, C.C.

    1988-01-01

    Contrary to the usual belief that MHD intermediate shocks are extraneous, the authors have recently shown by numerical solutions of dissipative MHD equations that intermediate shocks are admissible and can be formed through nonlinear steepening from a continuous wave. In this paper, he clarifies the differences between the conventional view and the results by studying the interaction of an MHD intermediate shock with an intermediate wave. The study reaffirms his results. In addition, the study shows that there exists a larger class of shocklike solutions in the time-dependent dissiaptive MHD equations than are given by the MHD Rankine-Hugoniot relations. it also suggests a mechanism for forming rotational discontinuities through the interaction of an intermediate shock with an intermediate wave. The results are of importance not only to the MHD shock theory but also to studies such as magnetic field reconnection models

  1. 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

    2008-01-01

    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...

  2. Reversible formation of high-valent-iron-oxo-porphyrin intermediate in heme-based catalysis: revisiting the kinetic model for horseradish peroxidase.

    NARCIS (Netherlands)

    Haandel, van M.J.H.; Primus, J.L.; Teunis, C.; Boersma, M.G.; Osman, A.M.; Veeger, C.; Rietjens, I.M.C.M.

    1998-01-01

    Many heme-containing biocatalysts exert their catalytic action through the initial formation of so-called high-valent-iron-oxo porphyrin intermediates. For horseradish peroxidase the initial intermediate formed has been identified as a high-valent-iron-oxo porphyrin π-radical cation, called compound

  3. Afrikaans Syllabification Patterns

    Directory of Open Access Journals (Sweden)

    Tilla Fick

    2010-01-01

    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

  4. Single Vs Mixed Organic Cation for Low Temperature Processed Perovskite Solar Cells

    International Nuclear Information System (INIS)

    Mahmud, Md Arafat; Elumalai, Naveen Kumar; Upama, Mushfika Baishakhi; Wang, Dian; Wright, Matthew; Chan, Kah Howe; Xu, Cheng; Haque, Faiazul; Uddin, Ashraf

    2016-01-01

    Highlights: • Low temperature processed ZnO based single & mixed organic cation perovskite device. • 37% higher PCE in mixed cation perovskite solar cells (PSCs) than single cation ones. • Mixed cation PSCs exhibit significantly reduced photocurrent hysteresis. • Mixed cation PSCs demonstrate three fold higher device stability than single cation PSCs. • Electronic properties are analyzed using Electrochemical Impedance Spectroscopy. - Abstract: The present work reports a comparative study between single and mixed organic cation based MAPbI 3 and MA 0.6 FA 0.4 PbI 3 perovskite devices fabricated in conjunction with low temperature processed (<150 °C) ZnO electron transport layers. MA 0.6 FA 0.4 PbI 3 perovskite devices demonstrate 37% higher power conversion efficiency compared to MAPbI 3 perovskite devices developed on the ZnO ETL. In addition, MA 0.6 FA 0.4 PbI 3 devices exhibit very low photocurrent hysteresis and they are three-fold more stable than conventional MAPbI 3 PSCs (perovskite solar cells). An in-depth analysis on the charge transport properties in both fresh and aged devices has been carried out using electrochemical impedance spectroscopy analysis to comprehend the enhanced device stability of the mixed perovskite devices developed on the ZnO ETL. The study also investigates into the interfacial charge transfer characteristics associated with the ZnO/mixed organic cation perovskite interface and concomitant influence on the inherent electronic properties.

  5. Formation of radical cations in a model for the metabolism of aromatic hydrocarbons

    International Nuclear Information System (INIS)

    Lehner, Andreas F.; Horn, Jamie; Flesher, James W.

    2004-01-01

    To test the hypothesis that electrophilic radical cations are the major ultimate electrophilic and carcinogenic forms of benz[a]anthracene (BA), dibenz[a,h]anthracene (DBA), and benzo[a]pyrene (BP), we have focused on a chemical model of metabolism which parallels and duplicates known or potential metabolites of some polycyclic hydrocarbons formed in cells. Studies of this model system show that radical cations are hardly formed, if at all, in the case of BA or DBA but are definitely formed in the cases of the carcinogen BP as well as the non-carcinogenic hydrocarbons, pyrene and perylene. We conclude that the carcinogenicities of BA, DBA, BP, pyrene, and perylene are independent of one-electron oxidation to radical cation intermediates

  6. Valence isomerization of hexamethyl(dewar benzene) radical cation. Pulse radiolytic investigation

    International Nuclear Information System (INIS)

    Gebicki, J.; Marcinek, A.; Mayer, J.

    1989-01-01

    Organic radical ions are important intermediates in a wide variety of electron-transfer reactions. Both the steady-state and time-resolved techniques have been extensively applied to probe various aspects of their chemistry. We have recently established that low-temperature pulse radiolysis can be successfully applied to the kinetic study of radical ion transformations with very low activation barriers. The target of the present investigation is the hexamethyl(Dewar benzene) (HMDB)-hexamethylbenzene (HMDB) system. Studies by the CIDNP technique indicated the presence of two distinguishable radical cations in the system HMDB-HMB. This view has not been supported by a nanosecond spectroscopic observation which failed to reveal any evidence for a radical cation other than HMB sm-bullet+ . The aim of this work is to present spectroscopic evidence for two different radical cations HMDB sm-bullet+ -HMB sm-bullet+ and the activation barrier for their interconversion

  7. Investigating radical cation chain processes in the electrocatalytic Diels-Alder reaction.

    Science.gov (United States)

    Imada, Yasushi; Okada, Yohei; Chiba, Kazuhiro

    2018-01-01

    Single electron transfer (SET)-triggered radical ion-based reactions have proven to be powerful options in synthetic organic chemistry. Although unique chain processes have been proposed in various photo- and electrochemical radical ion-based transformations, the turnover number, also referred to as catalytic efficiency, remains unclear in most cases. Herein, we disclose our investigations of radical cation chain processes in the electrocatalytic Diels-Alder reaction, leading to a scalable synthesis. A gram-scale synthesis was achieved with high current efficiency of up to 8000%. The reaction monitoring profiles showed sigmoidal curves with induction periods, suggesting the involvement of intermediate(s) in the rate determining step.

  8. 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: tolaymat.thabet@epa.gov [USEPA, Office of Research and Development, Cincinnati, OH (United States)

    2016-07-01

    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.

  9. Intermediate valence spectroscopy

    International Nuclear Information System (INIS)

    Gunnarsson, O.; Schoenhammer, K.

    1987-01-01

    Spectroscopic properties of intermediate valence compounds are studied using the Anderson model. Due to the large orbital and spin degeneracy N/sub f/ of the 4f-level, 1/N/sub f/ can be treated as a small parameter. This approach provides exact T = 0 results for the Anderson impurity model in the limit N/sub f/ → ∞, and by adding 1/N/sub f/ corrections some properties can be calculated accurately even for N/sub f/ = 1 or 2. In particular valence photoemission and resonance photoemission spectroscopies are studied. A comparison of theoretical and experimental spectra provides an estimate of the parameters in the model. Core level photoemission spectra provide estimates of the coupling between the f-level and the conduction states and of the f-level occupancy. With these parameters the model gives a fair description of other electron spectroscopies. For typical parameters the model predicts two structures in the f-spectrum, namely one structure at the f-level and one at the Fermi energy. The resonance photoemission calculation gives a photon energy dependence for these two peaks in fair agreement with experiment. The peak at the Fermi energy is partly due to a narrow Kondo resonance, resulting from many-body effects and the presence of a continuous, partly filled conduction band. This resonance is related to a large density of low-lying excitations, which explains the large susceptibility and specific heat observed for these systems at low temperatures. 38 references, 11 figures, 2 tables

  10. Welding. Performance Objectives. Intermediate Course.

    Science.gov (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)…

  11. Intermediate structure and threshold phenomena

    International Nuclear Information System (INIS)

    Hategan, Cornel

    2004-01-01

    The Intermediate Structure, evidenced through microstructures of the neutron strength function, is reflected in open reaction channels as fluctuations in excitation function of nuclear threshold effects. The intermediate state supporting both neutron strength function and nuclear threshold effect is a micro-giant neutron threshold state. (author)

  12. 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

    2008-12-18

    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.

  13. Cationic polymers and their therapeutic potential

    NARCIS (Netherlands)

    Samal, S.K.; Dash, M.; van Vlierberghe, S.; Kaplan, D.; Chiellini, E.; van Blitterswijk, Clemens; Moroni, Lorenzo; Dubruel, P.

    2012-01-01

    The last decade has witnessed enormous research focused on cationic polymers. Cationic polymers are the subject of intense research as non-viral gene delivery systems, due to their flexible properties, facile synthesis, robustness and proven gene delivery efficiency. Here, we review the most recent

  14. Tripodal Receptors for Cation and Anion Sensors

    Directory of Open Access Journals (Sweden)

    David N. Reinhoudt

    2006-08-01

    Full Text Available 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 are emphasised, along with their potential applications in optical sensors or optodes.

  15. Asymmetric Aminalization via Cation-Binding Catalysis

    DEFF Research Database (Denmark)

    Park, Sang Yeon; Liu, Yidong; Oh, Joong Suk

    2018-01-01

    Asymmetric cation-binding catalysis, in principle, can generate "chiral" anionic nucleophiles, where the counter cations are coordinated within chiral environments. Nitrogen-nucleophiles are intrinsically basic, therefore, its use as nucleophiles is often challenging and limiting the scope of the...

  16. Intermediate neutron spectrum problems and the intermediate neutron spectrum experiment

    International Nuclear Information System (INIS)

    Jaegers, P.J.; Sanchez, R.G.

    1996-01-01

    Criticality benchmark data for intermediate energy spectrum systems does not exist. These systems are dominated by scattering and fission events induced by neutrons with energies between 1 eV and 1 MeV. Nuclear data uncertainties have been reported for such systems which can not be resolved without benchmark critical experiments. Intermediate energy spectrum systems have been proposed for the geological disposition of surplus fissile materials. Without the proper benchmarking of the nuclear data in the intermediate energy spectrum, adequate criticality safety margins can not be guaranteed. The Zeus critical experiment now under construction will provide this necessary benchmark data

  17. Lithium ionophore VIII as an extraordinarily effective receptor for the strontium cation: Experimental and theoretical study

    Czech Academy of Sciences Publication Activity Database

    Makrlík, E.; Novák, Vít; Vaňura, P.; Bouř, Petr

    2014-01-01

    Roč. 1061, Mar 5 (2014), s. 110-113 ISSN 0022-2860 Institutional support: RVO:61388963 Keywords : strontium cation * lithium ionophore VIII * complexation * extraction and stability constants * DFT calculations * structures Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.602, year: 2014

  18. Complexation of the cesium cation with lithium ionophore VIII: extraction and DFT study

    Czech Academy of Sciences Publication Activity Database

    Makrlík, E.; Novák, Vít; Vaňura, P.; Bouř, Petr

    2013-01-01

    Roč. 298, č. 3 (2013), s. 2065-2068 ISSN 0236-5731 Institutional support: RVO:61388963 Keywords : cesium cation * lithium ionophore VIII * complexation * extraction and stability constants * water-nitrobenzene system * DFT calculations * structures Subject RIV: CB - Analytical Chemistry , Separation Impact factor: 1.415, year: 2013

  19. Complexing properties of some carbamoylmethylphosphine oxides and methylenediphosphine dioxides with respect to alkali metal cations and the effect of abnormal aryl strengthening

    International Nuclear Information System (INIS)

    Evreinov, V.I.; Safronova, Z.V.; Yarkevich, A.N.; Kharitonov, A.V.; Bondarenko, N.A.; Tsvetkov, E.N.

    1999-01-01

    By the method of conductometry in anhydrous tetrahydrofuran at 25 Deg C stability constants of alkali metal (M = Li, Na, K) cation complexes with certain phosphinoxides have been determined. Abnormal aryl strengthening is first of all pronounced in the cation complexes with tetraphenyldiphosphine dioxide [ru

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

    International Nuclear Information System (INIS)

    Valdés, Héctor; Alejandro, Serguei; Zaror, Claudio A.

    2012-01-01

    Highlights: ► Chemical and thermal treatment enhances catalytic activity of natural zeolite. ► Modified natural zeolite exhibits high stability after thermal treatment. ► Reducing the compensating cation content leads to an increase on ozone abatement. ► Surface active atomic oxygen was detected using the DRIFT technique. ► 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 −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 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Valdes, Hector, E-mail: hvaldes@ucsc.cl [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)

    2012-08-15

    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.

  2. Atomistic Modeling of Cation Diffusion in Transition Metal Perovskites La1-xSrxMnO3+/-δfor Solid Oxide Fuel Cell Cathodes Applications

    Science.gov (United States)

    Lee, Yueh-Lin; Duan, Yuhua; Morgan, Dane; Sorescu, Dan; Abernathy, Harry

    Cation diffusion in La1-xSrxMnO3+/-δ (LSM) and in related perovskite materials play an important role in controlling long term performance and stability of solid oxide fuel cell (SOFCs) cathodes. Due to sluggish rates of cation diffusion and complex coupling between defect chemistry and cation diffusion pathways, currently there is still lack of quantitative theoretical model predictions on cation diffusivity vs. T and P(O2) to describe experimental cation tracer diffusivities. In this work, based on ab initio modeling of LSM defect chemistry and migration barriers of the possible cation diffusion pathways, we assess the rates of A-site and B-site cation diffusion in a wide range of T and P(O2) at x =0.0 and 0.2 for SOFC applications. We demonstrate the active cation diffusion pathways in LSM involve cation defect clusters as cation transport carriers, where reduction in the cation migration barriers, which are governed by the steric effect associated with the metal-oxygen cage in the perovskite lattice, is much greater than the penalty of repulsive interaction in the A-site and B-site cation vacancy clusters, leading to higher cation diffusion rates as compared to those of single cation vacancy hopping mechanisms. The predicted Mn and La/Sr cation self-diffusion coefficients of LSM at at x =0.0 and 0.2 along with their 1/T and P(O2) dependences, are in good agreement with the experimental tracer diffusion coefficients.

  3. Concentration of ions Co(II), Ni(II) at the Tokem-250 carboxylic cation exchange for catalysts development

    Science.gov (United States)

    Zharkova, Valentina; Bobkova, Ludmila; Brichkov, Anton; Kozik, Vladimir

    2017-11-01

    Sorption and catalytic properties of the cation exchanger are investigated. It was found that the Tokem-250 has a wide operating range of pH. The value of the effective ionization constant of the functional groups of the cation exchanger (pKa) is 6.59. The Tokem-250 cation exchanger exhibits selectivity to Ni2+ ions to Co2+ (D˜103). This is probably due to the stability of ion-exchange complexes detected by the method of diffuse reflectance electron spectroscopy (ESDD). According to these data, for Co2+ ions, in contrast to Ni2+, tetragonal distortion of octahedral coordination is characteristic, which has a positive effect on the stability of complexes with Co2+. To obtain spherical catalysts on the basis of Tokem-250, cobalt-containing samples of cation exchanger were used. The developed spherical materials have catalytic activity in the reactions of deep and partial oxidation of n-heptane.

  4. Association Mechanisms of Unsaturated C2 Hydrocarbons with Their Cations: Acetylene and Ethylene

    Science.gov (United States)

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

    2013-01-01

    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.

  5. Infrared Spectroscopic and Theoretical Study of the HC_nO^+(N=5-12) Cations

    Science.gov (United States)

    Li, Wei; Jin, Jiaye; Wang, Guanjun; Zhou, Mingfei

    2017-06-01

    Carbon chains and derivatives are highly active species, which are widely existed as reactive intermediates in many chemical processes including atmospheric chemistry, hydrocarbon combustion, as well as interstellar chemistry. The carbon chain cations, HC_nO^+ (n = 5-12) are produced via pulsed laser vaporization of a graphite target in supersonic expansions containing carbon monoxide and hydrogen. The infrared spectra are measured via mass-selected infrared photodissociation spectroscopy of the CO "tagged" [HC_nO.CO] cation complexes in the 1600-3500 \\wn region. The geometries and electronic ground states of these cation complexes are determined by their infrared spectra in conjunction with theoretical calculations. All the HC_nO^+ (n = 5-12) core cations are characterized to be linear carbon chain derivatives terminated by hydrogen and oxygen. The HC_nO^+ cations with odd n have closed-shell singlet ground states with polyyne-like structures, while those with even n have triplet ground states with allene-like structures.

  6. Cation transport in isomeric pentanes

    International Nuclear Information System (INIS)

    Gyoergy, Istvan; Gee, Norman; Freeman, G.R.

    1985-01-01

    The cation mobility μsub(+) is measured in n-pentane, isopentane, neo-pentane, and mixtures of n- and neo-pentane over conditions from the normal liquid, through the critical fluid, to the low density gas. Most of the liquid data correlate with the reduced temperature T/Tsub(c). The T/Tsub(c) reflects free volume and viscosity changes. Comparison is made to neutral molecule diffusion. The transition from viscosity control of mobility in the liquid to density control in the dilute gas occurs over the reduced viscosity region 3 > eta/etasub(c) > 0.6, which corresponds to the reduced density region 1.9 > eta/etasub(c) > 0.5. In the saturated gas etaμsub(+) is similar in all pentanes, but iso- approximately> n- > neo-pentane. At constant density dμsub(+)/dT >= 0 for gases. The average gas nμsub(+) is similar in all pentanes, but iso- approximately> n- > neo-pentane. At constant density dμsub(+)/dT >= 0 for gases. The average momentum transfer cross sections in the n-/neo-pentane mixtures are similar to those in neo-pentane at low T but similar to those in n-pentane at high T. The present findings are combined with previous electron mobility data in addressing the effect of hydrocarbon molecular (external) shape on the electric breakdown strength of gases

  7. Cationic Bolaamphiphiles for Gene Delivery

    Science.gov (United States)

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

    2014-05-01

    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.

  8. Stressor states and the cation crossroads.

    Science.gov (United States)

    Weber, Karl T; Bhattacharya, Syamal K; Newman, Kevin P; Soberman, Judith E; Ramanathan, Kodangudi B; McGee, Jesse E; Malik, Kafait U; Hickerson, William L

    2010-12-01

    Neurohormonal activation involving the hypothalamic-pituitary-adrenal axis and adrenergic nervous and renin-angiotensin-aldosterone systems is integral to stressor state-mediated homeostatic responses. The levels of effector hormones, depending upon the degree of stress, orchestrate the concordant appearance of hypokalemia, ionized hypocalcemia and hypomagnesemia, hypozincemia, and hyposelenemia. Seemingly contradictory to homeostatic responses wherein the constancy of extracellular fluid would be preserved, upregulation of cognate-binding proteins promotes coordinated translocation of cations to injured tissues, where they participate in wound healing. Associated catecholamine-mediated intracellular cation shifts regulate the equilibrium between pro-oxidants and antioxidant defenses, a critical determinant of cell survival. These acute and chronic stressor-induced iterations in extracellular and intracellular cations are collectively referred to as the cation crossroads. Intracellular cation shifts, particularly excessive accumulation of Ca2+, converge on mitochondria to induce oxidative stress and raise the opening potential of their inner membrane permeability transition pores (mPTPs). The ensuing loss of cationic homeostasis and adenosine triphosphate (ATP) production, together with osmotic swelling, leads to organellar degeneration and cellular necrosis. The overall impact of iterations in extracellular and intracellular cations and their influence on cardiac redox state, cardiomyocyte survival, and myocardial structure and function are addressed herein.

  9. Cation effects on phosphatidic acid monolayers at various pH conditions.

    Science.gov (United States)

    Zhang, Ting; Cathcart, Matthew G; Vidalis, Andrew S; Allen, Heather C

    2016-10-01

    The impact of pH and cations on phase behavior, stability, and surface morphology for dipalmitoylphosphatidic acid (DPPA) monolayers was investigated. At pHCations are found to expand and stabilize the monolayer in the following order of increasing magnitude at pH 5.6: Na + >K + ∼Mg 2+ >Ca 2+ . Additionally, cation complexation is tied to the pH and protonation state of DPPA, which are the primary factors controlling the monolayer surface behavior. The binding affinity of cations to the headgroup and thus deprotonation capability of the cation, ranked in the order of Ca 2+ >Mg 2+ >Na + >K + , is found to be well explained by the law of matching water affinities. Nucleation of surface 3D lipid structures is observed from Ca 2+ , Mg 2+ , and Na + , but not from K + , consistent with the lowest binding affinity of K + . Unraveling cation and pH effects on DPPA monolayers is useful in further understanding the surface properties of complex systems such as organic-coated marine aerosols where organic films are directly influenced by the pH and ionic composition of the underlying aqueous phase. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  10. Enhanced desorption of Cs from clays by a polymeric cation-exchange agent

    Energy Technology Data Exchange (ETDEWEB)

    Park, Chan Woo, E-mail: park85@gmail.com [Decontamination & Decommissioning Research Division, Korea Atomic Energy Research Institute, Daedeok-daero 989-111, Yuseong-gu, Daejeon (Korea, Republic of); Kim, Bo Hyun [Decontamination & Decommissioning Research Division, Korea Atomic Energy Research Institute, Daedeok-daero 989-111, Yuseong-gu, Daejeon (Korea, Republic of); Department of Chemical Engineering, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon (Korea, Republic of); Yang, Hee-Man; Seo, Bum-Kyoung [Decontamination & Decommissioning Research Division, Korea Atomic Energy Research Institute, Daedeok-daero 989-111, Yuseong-gu, Daejeon (Korea, Republic of); Lee, Kune-Woo, E-mail: nkwlee@kaeri.re.kr [Decontamination & Decommissioning Research Division, Korea Atomic Energy Research Institute, Daedeok-daero 989-111, Yuseong-gu, Daejeon (Korea, Republic of)

    2017-04-05

    Highlights: • A cationic polyelectrolyte has excellent ability to desorb Cs bound strongly to clay. • The polycation desorbed significantly more Cs from the clay than did single cations. • Additional NH{sub 4}{sup +} treatment following the polycation treatment enhanced desorption of Cs. • The reaction yielded efficient desorption (95%) of an extremely low concentration of Cs-137 in the clay. - Abstract: We report on a new approach to increase the removal of cesium from contaminated clays based on the intercalation of a cationic polyelectrolyte into the clay interlayers. A highly charged cationic polyelectrolyte, polyethyleneimine (PEI), was shown to intercalate into the negatively charged interlayers and readily replaced Cs ions adsorbed on the interlayers of montmorillonite. The polycation desorbed significantly more Cs strongly bound to the clay than did single cations. Moreover, additional NH{sub 4}{sup +} treatment following the PEI treatment enhanced desorption of Cs ions that were less accessible by the bulky polyelectrolyte. This synergistic effect of PEI with NH{sub 4}{sup +} yielded efficient desorption (95%) of an extremely low concentration of radioactive {sup 137}Cs in the clay, which is very difficult to remove by simple cation-exchange methods due to the increased stability of the binding of Cs to the clay at low Cs concentrations.

  11. Influence of cations and anions on the formation of β-FeOOH

    International Nuclear Information System (INIS)

    Kamimura, T.; Nasu, S.; Segi, T.; Tazaki, T.; Miyuki, H.; Morimoto, S.; Kudo, T.

    2005-01-01

    In the presence of cations such as Cr 3+ , Cu 2+ and Ni 2+ , and anions such as SO 4 2- and NO 3 - , precipitation of β-FeOOH from Fe 3+ -solution containing Cl - by hydrolysis have been investigated by means of X-ray diffraction technique (XRD), Mossbauer spectroscopy (MS) and transmission electron microscopy (TEM). XRD peaks of β-FeOOH were broadened when the cations were added as sulfates, and this tendency for Cr 3+ was significantly observed. When the cations were added as nitrates, there was no significant change in XRD peaks. Inductively coupled plasma (ICP) analysis showed that only Cr added as sulfate was contained in β-FeOOH. Ni and Cu added as sulfates, and any cations added as nitrates were not contained in it. When β-FeOOH was synthesized with Na 2 SO 4 , the XRD peaks were broadened. XRD-peak broadening was mainly caused by the coexistence of SO 4 2- ion. The incorporation of cations in β-FeOOH is affected by coexistent anions, and the XRD-peak broadening is caused by not only cations but also anions. This behavior has been discussed in association with the stability of Fe 3+ -complexes in the solution

  12. A New Alkali-Stable Phosphonium Cation Based on Fundamental Understanding of Degradation Mechanisms.

    Science.gov (United States)

    Zhang, Bingzi; Kaspar, Robert B; Gu, Shuang; Wang, Junhua; Zhuang, Zhongbin; Yan, Yushan

    2016-09-08

    Highly alkali-stable cationic groups are a critical component of hydroxide exchange membranes (HEMs). To search for such cations, we studied the degradation kinetics and mechanisms of a series of quaternary phosphonium (QP) cations. Benzyl tris(2,4,6-trimethoxyphenyl)phosphonium [BTPP-(2,4,6-MeO)] was determined to have higher alkaline stability than the benchmark cation, benzyl trimethylammonium (BTMA). A multi-step methoxy-triggered degradation mechanism for BTPP-(2,4,6-MeO) was proposed and verified. By replacing methoxy substituents with methyl groups, a superior QP cation, methyl tris(2,4,6-trimethylphenyl)phosphonium [MTPP-(2,4,6-Me)] was developed. MTPP-(2,4,6-Me) is one of the most stable cations reported to date, with <20 % degradation after 5000 h at 80 °C in a 1 m KOD in CD3 OD/D2 O (5:1 v/v) solution. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Intermediate Levels of Visual Processing

    National Research Council Canada - National Science Library

    Nakayama, Ken

    1998-01-01

    ...) surface representation, here we have shown that there is an intermediate level of visual processing, between the analysis of the image and higher order representations related to specific objects; (2...

  14. Cation distributions on rapidly solidified cobalt ferrite

    Science.gov (United States)

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

    1990-01-01

    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.

  15. Radioimmunoassay of human eosinophil cationic protein

    International Nuclear Information System (INIS)

    Venge, P.; Roxin, L.E.; Olsson, I.

    1977-01-01

    A radioimmunosorbent assay has been developed which allows the detection in serum of a cationic protein derived from eosinophil granulocytes. In 34 healthy individuals the mean level was 31 μg/l. with a range of 5 to 55 μg/l. The serum concentration of 'eosinophil' cationic protein was correlated (P<0.001) to the number of eosinophil granulocytes in peripheral blood. Quantitiation of 'eosinophil' cationic protein in serum might be useful in the study of eosinophil granulocyte turnover and function in vivo. (author)

  16. Mechanisms of deterioration of intermediate moisture food systems

    Science.gov (United States)

    Labuza, T. P.

    1972-01-01

    A study of shelf stability in intermediate moisture foods was made. Major efforts were made to control lipid oxidation and nonenzymatic browning. In order to determine means of preventing these reactions, model systems were developed having the same water activity content relationship of intermediate moisture foods. Models were based on a cellulose-lipid and protein-lipid system with glycerol added as the humectant. Experiments with both systems indicate that lipid oxidation is promoted significantly in the intermediate moisture range. The effect appeared to be related to increased mobility of either reactants or catalysts, since when the amount of water in the system reached a level where capillary condensation occurred and thus free water was present, the rates of oxidation increased. With added glycerol, which is water soluble and thus increases the amount of mobile phase, the increase in oxidation rate occurs at a lower relative humidity. The rates of oxidation were maximized at 61% RH and decreased again at 75% RH probably due to dilution. No significant non-enzymatic browning occurred in the protein-lipid systems. Prevention of oxidation by the use of metal chelating agents was enhanced in the cellulose system, whereas, with protein present, the lipid soluble chain terminating antioxidants (such as BHA) worked equally as well. Preliminary studies of foods adjusted to the intermediate moisture range bear out the results of oxidation in model systems. It can be concluded that for most fat containing intermediate moisture foods, rancidity will be the reaction most limiting stability.

  17. Cationization of heparin for film applications

    Czech Academy of Sciences Publication Activity Database

    Šimkovic, I.; Mendichi, R.; Kelnar, Ivan; Filip, J.; Hricovíni, M.

    2015-01-01

    Roč. 115, 22 January (2015), s. 551-558 ISSN 0144-8617 Institutional support: RVO:61389013 Keywords : heparin * cationization * NMR Subject RIV: CD - Macromolecular Chemistry Impact factor: 4.219, year: 2015

  18. Cycloaliphatic epoxide resins for cationic UV - cure

    International Nuclear Information System (INIS)

    Verschueren, K.; Balwant Kaur

    1999-01-01

    This paper introduces the cyclo - aliphatic epoxide resins used for the various applications of radiation curing and their comparison with acrylate chemistry. Radiation curable coatings and inks are pre - dominantly based on acrylate chemistry but over the last few years, cationic chemistry has emerged successfully with the unique properties inherent with cyclo - aliphatic epoxide ring structures. Wide variety of cationic resins and diluents, the formulation techniques to achieve the desired properties greatly contributes to the advancement of UV - curing technology

  19. Chemical reactivity of cation-exchanged zeolites

    OpenAIRE

    Pidko, E.A.

    2008-01-01

    Zeolites modified with metal cations have been extensively studied during the last two decades because of their wide application in different technologically important fields such as catalysis, adsorption and gas separation. Contrary to the well-understood mechanisms of chemical reactions catalyzed by Brønsted acid sites in the hydrogen forms of zeolites, the nature of chemical reactivity, and related, the structure of the metal-containing ions in cation-exchanged zeolites remains the subject...

  20. Restructuring of a peat in interaction with multivalent cations: effect of cation type and aging time.

    Science.gov (United States)

    Kunhi Mouvenchery, Yamuna; Jaeger, Alexander; Aquino, Adelia J A; Tunega, Daniel; Diehl, Dörte; Bertmer, Marko; Schaumann, Gabriele Ellen

    2013-01-01

    It is assumed to be common knowledge that multivalent cations cross-link soil organic matter (SOM) molecules via cation bridges (CaB). The concept has not been explicitly demonstrated in solid SOM by targeted experiments, yet. Therefore, the requirements for and characteristics of CaB remain unidentified. In this study, a combined experimental and molecular modeling approach was adopted to investigate the interaction of cations on a peat OM from physicochemical perspective. Before treatment with salt solutions of Al(3+), Ca(2+) or Na(+), respectively, the original exchangeable cations were removed using cation exchange resin. Cation treatment was conducted at two different values of pH prior to adjusting pH to 4.1. Cation sorption is slower (>2 h) than deprotonation of functional groups (cation addition and decreased with increasing cation valency. Sorption coefficients were similar for all cations and at both pH. This contradicts the general expectations for electrostatic interactions, suggesting that not only the interaction chemistry but also spatial distribution of functional groups in OM determines binding of cations in this peat. The reaction of contact angle, matrix rigidity due to water molecule bridges (WaMB) and molecular mobility of water (NMR analysis) suggested that cross-linking via CaB has low relevance in this peat. This unexpected finding is probably due to the low cation exchange capacity, resulting in low abundance of charged functionalities. Molecular modeling demonstrates that large average distances between functionalities (∼3 nm in this peat) cannot be bridged by CaB-WaMB associations. However, aging strongly increased matrix rigidity, suggesting successive increase of WaMB size to connect functionalities and thus increasing degree of cross-linking by CaB-WaMB associations. Results thus demonstrated that the physicochemical structure of OM is decisive for CaB and aging-induced structural reorganisation can enhance cross-link formation.

  1. Study of radionuclides complexes formation by organic compounds in intermediate and low-level radioactive wastes; Etude de la mobilisation, par des complexants organiques, des radionucleides contenus dans les dechets radioactifs de faible et moyenne activite

    Energy Technology Data Exchange (ETDEWEB)

    Bourbon, X.

    1994-12-01

    In the general framework of the safety of nuclear wastes of low and intermediate activity, we studied the effects of organic compounds on the solubilization of metallic cations. Organic compounds originate from the degradation of cellulose in concrete interstitial waters. Degradation reactions generate a number of products, among which carboxylic acids. These acids are known for their chelating properties. We first analysed the degradation of cellulose in alkaline conditions: we qualitatively and quantitatively determined the degradation products for various reaction progress indices, including a dozen of carboxylic acids. The principal goal of our work was the prediction of the behaviour of metallic cations in such cellulose degradation solutions. Owing the complexity of the system, a priori theoretical calculation are not possible. We have thus decided to choose tetra hydroxy pentanoic acid as a reference compound in order to simulate as accurately as possible the behaviour of more complex acids which contain similar functional groups. We have experimentally determined the complexing properties of this reference acid toward divalent cobalt and copper, and trivalent samarium and europium. Simple and mixed complex (hydroxyl) have been evidenced in alkaline medium. Their stability constants have been determined and extrapolated at zero ionic strength using the SIT theory. These results allowed us to theoretically predict the behaviour of our four reference cations in cellulose degradation products formed in concrete interstitial waters. In parallel, we have measured their solubility in real cellulose degradation solutions. Solubility predictions are correct for transition metals, but not for rare earth cations. In this case the complexes which have been identified with tetra hydroxy pentanoic acid are not stable enough to dissolve metallic hydroxides. In real degradation solutions, other compounds would account for the enhancement of rare earth elements solubility.

  2. Formation of radical cations of diaryloxadiazoles

    International Nuclear Information System (INIS)

    Helmstreit, W.

    1988-01-01

    The nature of the formation of the radical cation of the 2,5-bis-(p-diethylaminophenyl)-1,3,4-oxadiazole (PC) in liquid n-butyl chloride and acetonitrile has been investigated by observing excited state fluorescence and transient absorption using nanosecond pulse radiolysis and laser flash photolysis. The formation of solute oxonium ions has also been observed. At concentrations -4 mol dm -3 the growth time at which the transient absorption of the radical cation reaches the maximum follows the rise time of the electron pulse ( 2 laser yields the solute radical cation in an acetonitrile solution of 2 x 10 -4 mol dm -3 PC via an electronically excited state. Here, the generation time was smaller than 5 ns. The yield of the cation is increased by addition of CCl 4 . A reaction mechanism is proposed that explains the fast cation formation in terms of an exciplex formed by interaction between an electronically excited state of diaryloxadiazole and the ground state of the solvent. This exciplex yields the solute radical cation. (author)

  3. Luminescent sulfides of monovalent and trivalent cations

    International Nuclear Information System (INIS)

    1975-01-01

    The invention discloses a family of luminescent materials or phosphors having a rhombohedral crystal structure and consisting essentially of a mixed host sulfide of at least one monovalent host cation and at least one trivalent host cation, and containing, for each mole of phosphor, 0.0005 to 0.05 mole of at least one activating cation. The monovalent host cations may be Na, K or Rb and Cs. The trivalent host cations may be Gd, La, Lu, Sc and Y. The activating cations may be one or more of trivalent As, Bi, Ce, Dy, Er, Pr, Sb, Sm, Tb and Tm; divalent Lu, Mn, Pb and Sn; and monovalent Ag, Cu and Tl. The novel phosphors may be used in devices to convert electron-beam, ultraviolet or x-ray energy to light in the visible spectrum. Such energy conversion can be employed for example in fluoroscopic screens, and in viewing screens of cathode-ray tubes and other electron tubes

  4. Divalent cation shrinks DNA but inhibits its compaction with trivalent cation.

    Science.gov (United States)

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

    2016-05-28

    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.

  5. Intermediate state trapping of a voltage sensor

    DEFF Research Database (Denmark)

    Lacroix, Jérôme J; Pless, Stephan Alexander; Maragliano, Luca

    2012-01-01

    Voltage sensor domains (VSDs) regulate ion channels and enzymes by undergoing conformational changes depending on membrane electrical signals. The molecular mechanisms underlying the VSD transitions are not fully understood. Here, we show that some mutations of I241 in the S1 segment of the Shaker...... Kv channel positively shift the voltage dependence of the VSD movement and alter the functional coupling between VSD and pore domains. Among the I241 mutants, I241W immobilized the VSD movement during activation and deactivation, approximately halfway between the resting and active states......, and drastically shifted the voltage activation of the ionic conductance. This phenotype, which is consistent with a stabilization of an intermediate VSD conformation by the I241W mutation, was diminished by the charge-conserving R2K mutation but not by the charge-neutralizing R2Q mutation. Interestingly, most...

  6. Physics of intermediate shocks: A review

    Science.gov (United States)

    Karimabadi, H.

    1995-01-01

    Intermediate shocks (ISs) lead to a transition from super-Alfvenic to sub-Alfvenic flow and are different from slow and fast shocks in that an IS rotates the component of the magnetic field tangent to the shock plane by 180 deg. Another peculiarity of ISs is that for the same upstream conditions an IS can have two different downstream states. There also exist a second class of ISs which rotate the magnetic field by an angle other than 180 deg. Due to their noncoplanar nature they cannot be time-stationary and are referred to as time-dependent intermediate shocks (TDIS). The existence of ISs has been the subject of much controversy over the years. Early studies questioned the physical reality of ISs. However, the studies of ISs found a new impetus when C.C. Wu showed that ISs do exist and are stable within the resistive MHD framework. In this paper, after a brief historical overview of the subject, we will review the latest developments in the study of ISs. In particular, we will address the questions of stability and structure of ISs and the relationship between ISs and other discontinuities. One of the recent developments has been the finding that ISs can be unsteady, reforming in time. Details of this process will be discussed. Finally, we examine the effect of anisotropy on the resolutions and discuss the relevance of ISs to the observed field rotations at the Earth's magnetopause.

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

    KAUST Repository

    Rouen, Mathieu

    2014-09-11

    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. Brillouin spectroscopy with surface acoustic waves on intermediate valent, doped SmS

    International Nuclear Information System (INIS)

    Schaerer, U.; Jung, A.; Wachter, P.

    1998-01-01

    Brillouin scattering on surface acoustic waves is a very powerful tool to determine the elastic constants of intermediate valent crystals, since the method is non-destructive and no mechanical contact is needed. A strong evidence for intermediate valence is a negative value of Poisson's ratio, which describes the behavior of the volume under uniaxial pressure. SmS by itself makes a semiconductor-metal transition at a pressure of more than 6.5 kbar. When substituting the divalent Sm by a trivalent cation, like Y, La or Tm, SmS can become - depending on the doping concentration - intermediate valent without any applied, external pressure. In this work, we will present measurements of the velocities of the surface acoustic waves and the calculation of the elastic constants of La- and Tm-doped SmS compounds. We found a clear dependence of Poisson's ratio on the doping concentration and on the valence of the materials. Furthermore, we will discuss the mechanism leading to intermediate valence when substituting Sm. Besides the internal, chemical pressure, which is produced by the built in trivalent cations with their smaller ionic radii, we have clear evidence, that the free electrons in the 5d band, induced by the substituting atoms, also play an important role in making doped SmS intermediate valent. (orig.)

  9. Search for intermediate vector bosons

    International Nuclear Information System (INIS)

    Cline, D.B.; Rubbia, C.; van der Meer, S.

    1982-01-01

    Over the past 15 years a new class of unified theories has been developed to describe the forces acting between elementary particles. The most successful of the new theories establishes a link between electromagnetism and the weak force. A crucial prediction of this unified electroweak theory is the existence of three massive particles called intermediate vector bosons. If these intermediate vector bosons exist and if they have properties attributed to them by electroweak theory, they should soon be detected, as the world's first particle accelerator with enough energy to create such particles has recently been completed at the European Organization for Nuclear Research (CERN) in Geneva. The accelerator has been converted to a colliding beam machine in which protons and antiprotons collide head on. According to electroweak theory, intermediate vector bosons can be created in proton-antiproton collisions. (SC)

  10. Search for intermediate vector bosons

    International Nuclear Information System (INIS)

    Klajn, D.B.; Rubbia, K.; Meer, S.

    1983-01-01

    Problem of registration and search for intermediate vector bosons is discussed. According to weak-current theory there are three intermediate vector bosons with +1(W + )-1(W - ) and zero (Z 0 ) electric charges. It was suggested to conduct the investigation into particles in 1976 by cline, Rubbia and Makintair using proton-antiproton beams. Major difficulties of the experiment are related to the necessity of formation of sufficient amount of antiparticles and the method of antiproton beam ''cooling'' for the purpose of reduction of its random movements. The stochastic method was suggested by van der Meer in 1968 as one of possible cooling methods. Several large detectors were designed for searching intermediate vector bosons

  11. Gravity with Intermediate Goods Trade

    Directory of Open Access Journals (Sweden)

    Sujin Jang

    2017-12-01

    Full Text Available This paper derives the gravity equation with intermediate goods trade. We extend a standard monopolistic competition model to incorporate intermediate goods trade, and show that the gravity equation with intermediates trade is identical to the one without it except in that gross output should be used as the output measure instead of value added. We also show that the output elasticity of trade is significantly underestimated when value added is used as the output measure. This implies that with the conventional gravity equation, the contribution of output growth can be substantially underestimated and the role of trade costs reduction can be exaggerated in explaining trade expansion, as we demonstrate for the case of Korea's trade growth between 1995 and 2007.

  12. Accelerators for forming cationic technetium complexes useful as radiodiagnostic images

    International Nuclear Information System (INIS)

    Tweedle, M.F.

    1985-01-01

    This invention relates to compositions for making cationic radiodiagnostic agents and, in particular, to accelerator compounds for labelling such cationic radiodiagnostic agents, kits for preparing such 99m Tc-labelled cationic radiodiagnostic agents with technetium, and methods for labelling such cationic radiodiagnostic agents with technetium

  13. Intermediate filaments and gene regulation.

    Science.gov (United States)

    Traub, P

    1995-01-01

    The biological role of intermediate filaments (IFs) of eukaryotic cells is still a matter of conjecture. On the basis of immunofluorescence and electron microscopic observations, they appear to play a cytoskeletal role in that they stabilize cellular structure and organize the distribution and interactions of intracellular organelles and components. The expression of a large number of cell type-specific and developmentally regulated subunit proteins is believed to provide multicellular organisms with different IF systems capable of differential interactions with the various substructures and components of their multiple, differentiated cells. However, the destruction of distinct IF systems by manipulation of cultured cells or by knock-out mutation of IF subunit proteins in transgenic mice exerts relatively little influence on cellular morphology and physiology and on development of mutant animals. In order to rationalize this dilemma, the cytoskeletal concept of IF function has been extended to purport that cytoplasmic (c) IFs and their subunit proteins also play fundamental roles in gene regulation. It is based on the in vitro capacity of cIF(protein)s to interact with guanine-rich, single-stranded DNA, supercoiled DNA and histones, as well as on their close structural relatedness to gene-regulatory DNA-binding and nuclear matrix proteins. Since cIF proteins do not possess classical nuclear localization signals, it is proposed that cIFs directly penetrate the double nuclear membrane, exploiting the amphiphilic, membrane-active character of their subunit proteins. Since they can establish metastable multisite contacts with nuclear matrix structures and/or chromatin areas containing highly repetitive DNA sequence elements at the nuclear periphery, they are supposed to participate in chromosome distribution and chromatin organization in interphase nuclei of differentiated cells. Owing to their different DNA-binding specificities, the various cIF systems may in this

  14. Dissecting Hofmeister Effects: Direct Anion-Amide Interactions Are Weaker than Cation-Amide Binding.

    Science.gov (United States)

    Balos, Vasileios; Kim, Heejae; Bonn, Mischa; Hunger, Johannes

    2016-07-04

    Whereas there is increasing evidence for ion-induced protein destabilization through direct ion-protein interactions, the strength of the binding of anions to proteins relative to cation-protein binding has remained elusive. In this work, the rotational mobility of a model amide in aqueous solution was used as a reporter for the interactions of different anions with the amide group. Protein-stabilizing salts such as KCl and KNO3 do not affect the rotational mobility of the amide. Conversely, protein denaturants such as KSCN and KI markedly reduce the orientational freedom of the amide group. Thus these results provide evidence for a direct denaturation mechanism through ion-protein interactions. Comparing the present findings with results for cations shows that in contrast to common belief, anion-amide binding is weaker than cation-amide binding. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  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

    2016-05-01

    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. Gas phase chemistry of N-benzylbenzamides with silver(I) cations: characterization of benzylsilver cation.

    Science.gov (United States)

    Sun, Hezhi; Jin, Zhe; Quan, Hong; Sun, Cuirong; Pan, Yuanjiang

    2015-03-07

    The benzylsilver cation which emerges from the collisional dissociation of silver(I)-N-benzylbenzamide complexes was characterized by deuterium-labeling experiments, theoretical calculations, breakdown curves and substituent effects. The nucleophilic attack of the carbonyl oxygen on an α-hydrogen results in the generation of the benzylsilver cation, which is competitive to the AgH loss with the α-hydrogen.

  17. Larval helminths in intermediate hosts

    DEFF Research Database (Denmark)

    Fredensborg, Brian Lund; Poulin, R

    2005-01-01

    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 ...

  18. Intermediate statistics in quantum maps

    Energy Technology Data Exchange (ETDEWEB)

    Giraud, Olivier [H H Wills Physics Laboratory, University of Bristol, Tyndall Avenue, Bristol BS8 1TL (United Kingdom); Marklof, Jens [School of Mathematics, University of Bristol, University Walk, Bristol BS8 1TW (United Kingdom); O' Keefe, Stephen [School of Mathematics, University of Bristol, University Walk, Bristol BS8 1TW (United Kingdom)

    2004-07-16

    We present a one-parameter family of quantum maps whose spectral statistics are of the same intermediate type as observed in polygonal quantum billiards. Our central result is the evaluation of the spectral two-point correlation form factor at small argument, which in turn yields the asymptotic level compressibility for macroscopic correlation lengths. (letter to the editor)

  19. Intermediality and the Child Performer

    Science.gov (United States)

    Budd, Natasha

    2016-01-01

    This report details examples of praxis in the creation and presentation of "Joy Fear and Poetry": an intermedial theatre performance in which children aged 7-12 years generated aesthetic gestures using a range of new media forms. The impetus for the work's development was a desire to make an intervention into habituated patterns of…

  20. Material Voices: Intermediality and Autism

    Science.gov (United States)

    Trimingham, Melissa; Shaughnessy, Nicola

    2016-01-01

    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…

  1. Effect of Divalent Cations on RED Performance and Cation Exchange Membrane Selection to Enhance Power Densities.

    Science.gov (United States)

    Rijnaarts, Timon; Huerta, Elisa; van Baak, Willem; Nijmeijer, Kitty

    2017-11-07

    Reverse electrodialysis (RED) is a membrane-based renewable energy technology that can harvest energy from salinity gradients. The anticipated feed streams are natural river and seawater, both of which contain not only monovalent ions but also divalent ions. However, RED using feed streams containing divalent ions experiences lower power densities because of both uphill transport and increased membrane resistance. In this study, we investigate the effects of divalent cations (Mg 2+ and Ca 2+ ) on RED and demonstrate the mitigation of those effects using both novel and existing commercial cation exchange membranes (CEMs). Monovalent-selective Neosepta CMS is known to block divalent cations transport and can therefore mitigate reductions in stack voltage. The new multivalent-permeable Fuji T1 is able to transport divalent cations without a major increase in resistance. Both strategies significantly improve power densities compared to standard-grade CEMs when performing RED using streams containing divalent cations.

  2. The adsorption of helium atoms on coronene cations

    Energy Technology Data Exchange (ETDEWEB)

    Kurzthaler, Thomas; Rasul, Bilal; Kuhn, Martin; Scheier, Paul, E-mail: Paul.Scheier@uibk.ac.at, E-mail: andrew.ellis@le.ac.uk [Institut für Ionenphysik und Angewandte Physik, Universität Innsbruck, Technikerstr. 25, A-6020 Innsbruck (Austria); Lindinger, Albrecht [Institut für Experimentalphysik, Freie Universität Berlin, Arnimallee 14, 14195 Berlin (Germany); Ellis, Andrew M., E-mail: Paul.Scheier@uibk.ac.at, E-mail: andrew.ellis@le.ac.uk [Department of Chemistry, University of Leicester, University Road, Leicester LE1 7RH (United Kingdom)

    2016-08-14

    We report the first experimental study of the attachment of multiple foreign atoms to a cationic polycyclic aromatic hydrocarbon (PAH). The chosen PAH was coronene, C{sub 24}H{sub 12}, which was added to liquid helium nanodroplets and then subjected to electron bombardment. Using mass spectrometry, coronene cations decorated with helium atoms were clearly seen and the spectrum shows peaks with anomalously high intensities (“magic number” peaks), which represent ion-helium complexes with added stability. The data suggest the formation of a rigid helium layer consisting of 38 helium atoms that completely cover both faces of the coronene ion. Additional magic numbers can be seen for the further addition of 3 and 6 helium atoms, which are thought to attach to the edge of the coronene. The observation of magic numbers for the addition of 38 and 44 helium atoms is in good agreement with a recent path integral Monte Carlo prediction for helium atoms on neutral coronene. An understanding of how atoms and molecules attach to PAH ions is important for a number of reasons including the potential role such complexes might play in the chemistry of the interstellar medium.

  3. Classical model of intermediate statistics

    International Nuclear Information System (INIS)

    Kaniadakis, G.

    1994-01-01

    In this work we present a classical kinetic model of intermediate statistics. In the case of Brownian particles we show that the Fermi-Dirac (FD) and Bose-Einstein (BE) distributions can be obtained, just as the Maxwell-Boltzmann (MD) distribution, as steady states of a classical kinetic equation that intrinsically takes into account an exclusion-inclusion principle. In our model the intermediate statistics are obtained as steady states of a system of coupled nonlinear kinetic equations, where the coupling constants are the transmutational potentials η κκ' . We show that, besides the FD-BE intermediate statistics extensively studied from the quantum point of view, we can also study the MB-FD and MB-BE ones. Moreover, our model allows us to treat the three-state mixing FD-MB-BE intermediate statistics. For boson and fermion mixing in a D-dimensional space, we obtain a family of FD-BE intermediate statistics by varying the transmutational potential η BF . This family contains, as a particular case when η BF =0, the quantum statistics recently proposed by L. Wu, Z. Wu, and J. Sun [Phys. Lett. A 170, 280 (1992)]. When we consider the two-dimensional FD-BE statistics, we derive an analytic expression of the fraction of fermions. When the temperature T→∞, the system is composed by an equal number of bosons and fermions, regardless of the value of η BF . On the contrary, when T=0, η BF becomes important and, according to its value, the system can be completely bosonic or fermionic, or composed both by bosons and fermions

  4. The fate of primary cations in radiolysis of alkanes as studied by ESR

    International Nuclear Information System (INIS)

    Iwasaki, M.; Toriyama, K.; Nunome, K.

    1983-01-01

    The structures and reactions of alkane cations (RH + ) have been studied by ESR to elucidate the fate of primary cations in radiolysis of alkanes. Radical cations of prototype alkanes such as C 2 H 6 , C 3 H 8 , iso-C 4 H 10 and neo-C 5 H 12 etc. as well as their partially deuterated analogues were stabilized in irradiated frozen matrices such as SF 6 , CFCl 2 CF 2 Cl and CFCl 3 having a higher ionization potential than that of these alkanes contained as dilute solutes. RH + in SF 6 and in CFCl 2 CF 2 Cl converts into alkyl radicals by deprotonation probably through bimolecular reactions, whereas RH + in CFCl 3 unimolecularily decomposes into olefinic cations by H 2 and/or CH 4 elimination reactions. It is further found that the electronic structures of propane and isobutane cations in halocarbon matrices are different from those in SF 6 and the difference is drastically reflected in the site preference of their deprotonation reactions. The results are discussed in relation to the mechanisms of pairwise formation of alkyl radicals in low temperature radiolysis of neat alkanes and its suppression by addition of electron scavengers. (author)

  5. Forging Colloidal Nanostructures via Cation Exchange Reactions.

    Science.gov (United States)

    De Trizio, Luca; Manna, Liberato

    2016-09-28

    Among the various postsynthesis treatments of colloidal nanocrystals that have been developed to date, transformations by cation exchange have recently emerged as an extremely versatile tool that has given access to a wide variety of materials and nanostructures. One notable example in this direction is represented by partial cation exchange, by which preformed nanocrystals can be either transformed to alloy nanocrystals or to various types of nanoheterostructures possessing core/shell, segmented, or striped architectures. In this review, we provide an up to date overview of the complex colloidal nanostructures that could be prepared so far by cation exchange. At the same time, the review gives an account of the fundamental thermodynamic and kinetic parameters governing these types of reactions, as they are currently understood, and outlines the main open issues and possible future developments in the field.

  6. Forging Colloidal Nanostructures via Cation Exchange Reactions

    Science.gov (United States)

    2016-01-01

    Among the various postsynthesis treatments of colloidal nanocrystals that have been developed to date, transformations by cation exchange have recently emerged as an extremely versatile tool that has given access to a wide variety of materials and nanostructures. One notable example in this direction is represented by partial cation exchange, by which preformed nanocrystals can be either transformed to alloy nanocrystals or to various types of nanoheterostructures possessing core/shell, segmented, or striped architectures. In this review, we provide an up to date overview of the complex colloidal nanostructures that could be prepared so far by cation exchange. At the same time, the review gives an account of the fundamental thermodynamic and kinetic parameters governing these types of reactions, as they are currently understood, and outlines the main open issues and possible future developments in the field. PMID:26891471

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

    Science.gov (United States)

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

    2016-09-14

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

  8. A Cation-containing Polymer Anion Exchange Membrane based on Poly(norbornene)

    Science.gov (United States)

    Beyer, Frederick; Price, Samuel; Ren, Xiaoming; Savage, Alice

    Cation-containing polymers are being studied widely for use as anion exchange membranes (AEMs) in alkaline fuel cells (AFCs) because AEMs offer a number of potential benefits including allowing a solid state device and elimination of the carbonate poisoning problem. The successful AEM will combine high performance from several orthogonal properties, having robust mechanical strength even when wet, high hydroxide conductivity, and the high chemical stability required for long device lifetimes. In this study, we have synthesized a model cationic polymer that combines three of the key advantages of Nafion. The polymer backbone based on semicrystalline atactic poly(norbornene) offers good mechanical properties. A flexible, ether-based tether between the backbone and fixed cation charged species (quaternary ammonium) should provide the low-Tg, hydrophilic environment required to facilitate OH- transport. Finally, methyl groups have been added at the beta position relative to the quaternary ammonium cation to prevent Hoffman elimination, one mechanism by which AEMs are neutralized in a high pH environment. In this poster, we will present our findings on mechanical properties, morphology, charge transport, and chemical stability of this material.

  9. Structure, thermodynamic and electronic properties of carbon-nitrogen cubanes and protonated polynitrogen cations

    Science.gov (United States)

    Chaban, Vitaly V.; Andreeva, Nadezhda A.

    2017-12-01

    Energy generation and storage are at the center of modern civilization. Energetic materials constitute quite a large class of compounds with a high amount of stored chemical energy that can be released. We hereby use a combination of quantum chemistry methods to investigate feasibility and properties of carbon-nitrogen cubanes and multi-charged polynitrogen cations in the context of their synthesis and application as unprecedented energetic materials. We show that the stored energy increases gradually with the nitrogen content increase. Nitrogen-poor cubanes retain their stabilities in vacuum, even at elevated temperatures. Such molecules will be probably synthesized at some point. In turn, polynitrogen cations are highly unstable, except N8H+, despite they are isoelectronic to all-carbon cubane. Kinetic stability of the cation decays drastically as its total charge increases. High-level thermodynamic calculations revealed that large amounts of energy are liberated upon decompositions of polynitrogen cations, which produce molecular nitrogen, acetylene, and protons. The present results bring a substantial insights to the design of novel high-energy compounds.

  10. Site preferences of actinide cations in [NZP] compounds

    Science.gov (United States)

    Hawkins, H. T.; Spearing, D. R.; Smith, D. M.; Hampel, F. G.; Veirs, D. K.; Scheetz, B. E.

    2000-07-01

    Compounds adopting the sodium dizirconium tris(phosphate) (NaZr2(PO4)3) structure type belong to the [NZP] structural family of compounds. [NZP] compounds possess desirable properties that would permit their application as hosts for the actinides. These properties include compositional flexibility (i.e., three structural sites that can accommodate a variety of different cations), high thermal stability, negligible thermal expansion, and resistance to radiation damage. Experimental data indicate that [NZP] compounds resist dissolution and release of constituents over a wide range of experimental conditions. Moreover, [NZP] compounds may be synthesized by both conventional and novel methods and may be heat treated or sintered at modest temperatures (800 °C-1350 °C) in open or restricted systems.

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

    Directory of Open Access Journals (Sweden)

    R. Nandini

    2010-01-01

    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.

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

    KAUST Repository

    Zhang, Hefeng

    2015-12-17

    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).

  13. Efficient scavenging of β-carotene radical cations by antiinflammatory salicylates

    DEFF Research Database (Denmark)

    Cheng, Hong; Liang, Ran; Han, Rui-Min

    2014-01-01

    by the anion of salicylic acid with 2.2 × 10 L mol s, but still of possible importance for light-exposed tissue. Surprisingly, acetylsalicylate, the aspirin anion, reacts with an intermediate rate in a reaction assigned to the anion of the mixed acetic-salicylic acid anhydride formed through base induced......The radical cation generated during photobleaching of β-carotene is scavenged efficiently by the anion of methyl salicylate from wintergreen oil in a second-order reaction approaching the diffusion limit with k = 3.2 × 10 L mol s in 9:1 v/v chloroform-methanol at 23 °C, less efficiently...... rearrangements. The relative scavenging rate of the β-carotene radical cation by the three salicylates is supported by DFT-calculations....

  14. Binding of Divalent Cations to Polygalacturonate: A Mechanism Driven by the Hydration Water.

    Science.gov (United States)

    Huynh, Uyen T D; Lerbret, Adrien; Neiers, Fabrice; Chambin, Odile; Assifaoui, Ali

    2016-02-11

    We have investigated the interactions between polygalacturonate (polyGal) and four divalent cations (M(2+) = Ba(2+), Ca(2+), Mg(2+), Zn(2+)) that differ in size and affinity for water. Our results evidence that M(2+)-polyGal interactions are intimately linked to the affinity of M(2+) for water. Mg(2+) interacts so strongly with water that it remains weakly bound to polyGal (polycondensation) by sharing water molecules from its first coordination shell with the carboxylate groups of polyGal. In contrast, the other cations form transient ionic pairs with polyGal by releasing preferentially one water molecule (for Zn(2+)) or two (for Ca(2+) and Ba(2+)), which corresponds to monodentate and bidentate binding modes with carboxylates, respectively. The mechanism for the binding of these three divalent cations to polyGal can be described by two steps: (i) monocomplexation and formation of point-like cross-links between polyGal chains (at low M(2+)/Gal molar ratios, R) and (ii) dimerization (at higher R). The threshold molar ratio, R*, between these two steps depends on the nature of divalent cations and is lower for calcium ions (R* 0.3). This difference may be explained by the intermediate affinity of Ca(2+) for water with respect to those of Zn(2+) and Ba(2+), which may induce the formation of cross-links of intermediate flexibility. By comparison, the lower and higher flexibilities of the cross-links formed by Zn(2+) and Ba(2+), respectively, may shift the formation of dimers to higher molar ratios (R*).

  15. Study on properties of cation-exchange membranes containing sulfonate groups

    International Nuclear Information System (INIS)

    Zu Jianhua; Wu Minghong; Qiu Shilong; Yao Side; Ye Yin

    2004-01-01

    Strong acid cation-exchange membranes were obtained by irradiation grafting of acrylic acid (AA) and sodium styrene sulfonate (SSS) onto high-density polyethylene (HDPE). Thermal and chemical stability of the cation-exchange membranes was investigated. The effectiveness of sulfonate-containing films was conformed in inducing high resistance to oxidative degradation. Thermal stability of the grafted HDPE was weaker than HDPE as detected by TGA analyzing technique. Char residue by TGA of the grafted HDPE is greater than that of HDPE. It shows that the branch chains including -SO 3 Na and -COOH was grafted onto the backbone of HDPE, and thus give a catalytic impetus to the charing. Crystallinity of the grafted membranes decreased with increasing grafting yield of the membrane samples. It is supposed that the decreased crystallinity is due to collective effects of the inherent crystallinity dilution by the amorphous grafted chains and disruption of spherulitic crystallites of the HDPE component

  16. Large guanidinium cation mixed with methylammonium in lead iodide perovskites for 19% efficient solar cells

    Science.gov (United States)

    Jodlowski, Alexander D.; Roldán-Carmona, Cristina; Grancini, Giulia; Salado, Manuel; Ralaiarisoa, Maryline; Ahmad, Shahzada; Koch, Norbert; Camacho, Luis; de Miguel, Gustavo; Nazeeruddin, Mohammad Khaja

    2017-12-01

    Organic-inorganic lead halide perovskites have shown photovoltaic performances above 20% in a range of solar cell architectures while offering simple and low-cost processability. Despite the multiple ionic compositions that have been reported so far, the presence of organic constituents is an essential element in all of the high-efficiency formulations, with the methylammonium and formamidinium cations being the sole efficient options available to date. In this study, we demonstrate improved material stability after the incorporation of a large organic cation, guanidinium, into the MAPbI3 crystal structure, which delivers average power conversion efficiencies over 19%, and stabilized performance for 1,000 h under continuous light illumination, a fundamental step within the perovskite field.

  17. Correlated Default and Financial Intermediation

    OpenAIRE

    Gregory Phelan

    2015-01-01

    Financial intermediation naturally arises when knowledge about the aggregate state is valuable for managing investments and lenders cannot easily observe the aggregate state. I show this using a costly enforcement model in which lenders need ex-post incentives to enforce payments from defaulted loans and borrowers' payoffs are correlated. When projects have correlated outcomes, learning the state of one project (via enforcement) provides information about the states of other projects. A large...

  18. Restructuring of a peat in interaction with multivalent cations: effect of cation type and aging time.

    Directory of Open Access Journals (Sweden)

    Yamuna Kunhi Mouvenchery

    Full Text Available It is assumed to be common knowledge that multivalent cations cross-link soil organic matter (SOM molecules via cation bridges (CaB. The concept has not been explicitly demonstrated in solid SOM by targeted experiments, yet. Therefore, the requirements for and characteristics of CaB remain unidentified. In this study, a combined experimental and molecular modeling approach was adopted to investigate the interaction of cations on a peat OM from physicochemical perspective. Before treatment with salt solutions of Al(3+, Ca(2+ or Na(+, respectively, the original exchangeable cations were removed using cation exchange resin. Cation treatment was conducted at two different values of pH prior to adjusting pH to 4.1. Cation sorption is slower (>>2 h than deprotonation of functional groups (<2 h and was described by a Langmuir model. The maximum uptake increased with pH of cation addition and decreased with increasing cation valency. Sorption coefficients were similar for all cations and at both pH. This contradicts the general expectations for electrostatic interactions, suggesting that not only the interaction chemistry but also spatial distribution of functional groups in OM determines binding of cations in this peat. The reaction of contact angle, matrix rigidity due to water molecule bridges (WaMB and molecular mobility of water (NMR analysis suggested that cross-linking via CaB has low relevance in this peat. This unexpected finding is probably due to the low cation exchange capacity, resulting in low abundance of charged functionalities. Molecular modeling demonstrates that large average distances between functionalities (∼3 nm in this peat cannot be bridged by CaB-WaMB associations. However, aging strongly increased matrix rigidity, suggesting successive increase of WaMB size to connect functionalities and thus increasing degree of cross-linking by CaB-WaMB associations. Results thus demonstrated that the physicochemical structure of OM is

  19. Double C-H activation of ethane by metal-free SO2*+ radical cations.

    Science.gov (United States)

    de Petris, Giulia; Cartoni, Antonella; Troiani, Anna; Barone, Vincenzo; Cimino, Paola; Angelini, Giancarlo; Ursini, Ornella

    2010-06-01

    The room-temperature C-H activation of ethane by metal-free SO(2)(*+) radical cations has been investigated under different pressure regimes by mass spectrometric techniques. The major reaction channel is the conversion of ethane to ethylene accompanied by the formation of H(2)SO(2)(*+), the radical cation of sulfoxylic acid. The mechanism of the double C-H activation, in the absence of the single activation product HSO(2)(+), is elucidated by kinetic studies and quantum chemical calculations. Under near single-collision conditions the reaction occurs with rate constant k=1.0 x 10(-9) (+/-30%) cm(3) s(-1) molecule(-1), efficiency=90%, kinetic isotope effect k(H)/k(D)=1.1, and partial H/D scrambling. The theoretical analysis shows that the interaction of SO(2)(*+) with ethane through an oxygen atom directly leads to the C-H activation intermediate. The interaction through sulfur leads to an encounter complex that rapidly converts to the same intermediate. The double C-H activation occurs by a reaction path that lies below the reactants and involves intermediates separated by very low energy barriers, which include a complex of the ethyl cation suitable to undergo H/D scrambling. Key issues in the observed reactivity are electron-transfer processes, in which a crucial role is played by geometrical constraints. The work shows how mechanistic details disclosed by the reactions of metal-free electrophiles may contribute to the current understanding of the C-H activation of ethane.

  20. Adsorption of cationic amylopectin on microcrystalline cellulose.

    NARCIS (Netherlands)

    Steeg, van de H.G.M.; Keizer, de A.; Cohen Stuart, M.A.; Bijsterbosch, B.H.

    1993-01-01

    The effects of electrolyte concentration and pH on the adsorption of cationic amylopectin on microcrystalline cellulose were investigated. The adsorbed amount in the pseudo-plateau of the isotherm showed a maximum as a function of the electrolyte concentration. We compared the data with a recent

  1. Alkynylcarbenium ions and related unsaturated cations

    Energy Technology Data Exchange (ETDEWEB)

    Lukyanov, Sergey M; Koblik, Alla V; Muradyan, Lyudmila A [Institute of Physical and Organic Chemistry, Rostov State University, Rostov-on-Don (Russian Federation)

    1998-10-31

    Published data on carbenium ions containing carbon-carbon triple bonds both directly conjugated with the carbenium centre and separated from it are surveyed and described systematically. Ammonium, diazonium, iminium, phosphonium and iodonium cations containing alkynyl groups, which can be regarded as heteroanalogues of alkynylcarbenium ions, are also considered. The bibliography includes 283 references.

  2. Alkynylcarbenium ions and related unsaturated cations

    International Nuclear Information System (INIS)

    Lukyanov, Sergey M; Koblik, Alla V; Muradyan, Lyudmila A

    1998-01-01

    Published data on carbenium ions containing carbon-carbon triple bonds both directly conjugated with the carbenium centre and separated from it are surveyed and described systematically. Ammonium, diazonium, iminium, phosphonium and iodonium cations containing alkynyl groups, which can be regarded as heteroanalogues of alkynylcarbenium ions, are also considered. The bibliography includes 283 references

  3. Effect of cations on the hydrated proton.

    Science.gov (United States)

    Ottosson, Niklas; Hunger, Johannes; Bakker, Huib J

    2014-09-17

    We report on a strong nonadditive effect of protons and other cations on the structural dynamics of liquid water, which is revealed using dielectric relaxation spectroscopy in the frequency range of 1-50 GHz. For pure acid solutions, protons are known to have a strong structuring effect on water, leading to a pronounced decrease of the dielectric response. We observe that this structuring is reduced when protons are cosolvated with salts. This reduction is exclusively observed for combinations of protons with other ions; for all studied solutions of cosolvated salts, the effect on the structural dynamics of water is observed to be purely additive, even up to high concentrations. We derive an empirical model that quantitatively describes the nonadditive effect of cosolvated protons and cations. We argue that the effect can be explained from the special character of the proton in water and that Coulomb fields exerted by other cations, in particular doubly charged cations like Mg(2+)aq and Ca(2+)aq, induce a localization of the H(+)aq hydration structures.

  4. 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...

  5. Cationic flotation of some lithium ores

    International Nuclear Information System (INIS)

    Valadao, G.E.S.; Peres, A.E.C.; Silva, H.C. da

    1984-01-01

    The cationic flotation of some lithium ores (spodumene, amblygonite, petalite, lepidolite) is studied by the measure of zeta potential and micro-flotation tests in Hallimond tube. The effect of some modifier agents (corn starch, meta sodium silicate) on the lithium flotation is studied. (M.A.C.) [pt

  6. Letter: OCCO*+, NNCO*+ and NNNN*+ radical cations.

    Science.gov (United States)

    Flammang, R; Srinivas, R; Nguyen, M T; Gerbaux, P

    2007-01-01

    Chemical ionization of a mixture of nitrogen and carbon monoxide produces three stable isobaric species at m/z 56: OCCO, OCNN and NNNN radical cations. Separated at increased resolution, these ions are readily identified by collisional activation. Neutralization-reionization experiments performed on two different mass spectrometers have not allowed the detection of any recovery signals for the corresponding neutrals.

  7. Al cation induces aggregation of serum proteins.

    Science.gov (United States)

    Chanphai, P; Kreplak, L; Tajmir-Riahi, H A

    2017-07-15

    Al cation is known to induce protein fibrillation and causes several neurodegenerative disorders. We report the spectroscopic, thermodynamic analysis and AFM imaging for the Al cation binding process with human serum albumin (HSA), bovine serum albumin (BSA) and milk beta-lactoglobulin (b-LG) in aqueous solution at physiological pH. Hydrophobicity played a major role in Al-protein interactions with more hydrophobic b-LG forming stronger Al-protein complexes. Thermodynamic parameters ΔS, ΔH and ΔG showed Al-protein bindings occur via hydrophobic and H-bonding contacts for b-LG, while van der Waals and H-bonding interactions prevail in HSA and BSA adducts. AFM clearly indicated that aluminum cations are able to force BSA and b-LG into larger or more robust aggregates than HSA, with HSA 4±0.2 (SE, n=801) proteins per aggregate, for BSA 17±2 (SE, n=148), and for b-LG 12±3 (SE, n=151). Thioflavin T test showed no major protein fibrillation in the presence of Al cation. Al complexation induced major alterations of protein conformations with the order of perturbations b-LG>BSA>HSA. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Chemical reactivity of cation-exchanged zeolites

    NARCIS (Netherlands)

    Pidko, E.A.

    2008-01-01

    Zeolites modified with metal cations have been extensively studied during the last two decades because of their wide application in different technologically important fields such as catalysis, adsorption and gas separation. Contrary to the well-understood mechanisms of chemical reactions catalyzed

  9. Cation-Dependent Light-Induced Halide Demixing in Hybrid Organic-Inorganic Perovskites

    OpenAIRE

    Sutter-Fella, CM; Ngo, QP; Cefarin, N; Gardener, K; Tamura, N; Stan, CV; Drisdell, WS; Javey, A; Toma, FM; Sharp, ID

    2018-01-01

    © 2018 American Chemical Society. Mixed cation metal halide perovskites with increased power conversion efficiency, negligible hysteresis, and improved long term stability under illumination, moisture, and thermal stressing have emerged as promising compounds for photovoltaic and optoelectronic applications. Here, we shed light on photo-induced halide demixing using in-situ photoluminescence spectroscopy and in-situ synchrotron X-ray diffraction (XRD) to directly compare the evolution of comp...

  10. Selective crystallization of cations with crown ethers

    International Nuclear Information System (INIS)

    Heffels, Dennis Egidius

    2014-01-01

    The aim of this work was to study the selectivity and preferences of the incorporation of differently sized cations in the cavities of various crown ethers and the characterization of the resulting compounds. The coordination preferences of crown ethers with different cavities have long been known, and the impact of other effects on the structure formation have increasingly become the focus of attention. In this work a comparative overview of the coordination preferences depending on various factors was undertaken. The focus was mainly on the variation of the cavity of the crown ether in the presence of differently sized cations. In addition, the effects of the solvent and differently coordinating anions have been investigated. Within the framework of this work, basic coordination preferences could be detected with rare earth nitrates, which are affected particularly by the choice of the solvent. The formation of different types of structures could be controlled by varying the conditions such that the incorporation of the cation in the cavity of the crown ether was influenced and the formation of a particular type of structure can be influenced partly by the choice of solvent. In this case no direct preferences for the incorporation into the cavity of the crown ether in relation to the cation size were observed for rare earth cations. However, the coordination of the crown ether leads in each case - for lanthanides - to rather high coordination numbers. A total of five new rare earth complexes and two structural variants could be observed with crown ethers. In the study of the selectivity of the incorporation into the cavity, known structures were also reproduced and further structures were characterized but the crystal structures not entirely solved. With the use of monovalent cations such as potassium, lithium or silver a total of nine new compounds could be synthesized, while no clear preferences for the incorporation of certain cations were detected. The

  11. MHD intermediate shock discontinuities: Pt. 1

    International Nuclear Information System (INIS)

    Kennel, C.F.; Blandford, R.D.; Coppi, P.

    1989-01-01

    Recent numerical investigations have focused attention once more on the role of intermediate shocks in MHD. Four types of intermediate shock are identified using a graphical representation of the MHD Rankine-Hugoniot conditions. This same representation can be used to exhibit the close relationship of intermediate shocks to switch-on shocks and rotational discontinuities. The conditions under which intermediate discontinuities can be found are elucidated. The variations in velocity, pressure, entropy and magnetic-field jumps with upstream parameters in intermediate shocks are exhibited graphically. The evolutionary arguments traditionally advanced against intermediate shocks may fail because the equations of classical MHD are not strictly hyperbolic. (author)

  12. Covalent functionalization of graphene with reactive intermediates.

    Science.gov (United States)

    Park, Jaehyeung; Yan, Mingdi

    2013-01-15

    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

  13. Cable Stability

    Energy Technology Data Exchange (ETDEWEB)

    Bottura, L [European Organization for Nuclear Research, Geneva (Switzerland)

    2014-07-01

    Superconductor stability is at the core of the design of any successful cable and magnet application. This chapter reviews the initial understanding of the stability mechanism, and reviews matters of importance for stability such as the nature and magnitude of the perturbation spectrum and the cooling mechanisms. Various stability strategies are studied, providing criteria that depend on the desired design and operating conditions.

  14. Structure relationship of cationic lipids on gene transfection mediated by cationic liposomes.

    Science.gov (United States)

    Paecharoenchai, Orapan; Niyomtham, Nattisa; Apirakaramwong, Auayporn; Ngawhirunpat, Tanasait; Rojanarata, Theerasak; Yingyongnarongkul, Boon-ek; Opanasopit, Praneet

    2012-12-01

    The aim of this study was to investigate the transfection efficiency of cationic liposomes formulated with phosphatidylcholine (PC) and novel synthesized diethanolamine-based cationic lipids at a molar ratio of 5:1 in comparison with Lipofectamine™ 2000. Factors affecting transfection efficiency and cell viability, including the chemical structure of the cationic lipids, such as different amine head group (diamine and polyamine; and non-spermine and spermine) and acyl chain lengths (C14, C16, and C18) and the weight ratio of liposomes to DNA were evaluated on a human cervical carcinoma cell line (HeLa cells) using the pDNA encoding green fluorescent protein (pEGFP-C2). Characterizations of these lipoplexes in terms of size and charge measurement and agarose gel electrophoresis were performed. The results from this study revealed that almost no transfection was observed in the liposome formulations composed of cationic lipids with a non-spermine head group. In addition, the transfection efficiency of these cationic liposomes was in the following order: spermine-C14 > spermine-C16 > spermine-C18. The highest transfection efficiency was observed in the formulation of spermine-C14 liposomes at a weight ratio of 25; furthermore, this formulation was safe for use in vitro. In conclusion, cationic liposomes containing spermine head groups demonstrated promising potential as gene carriers.

  15. Role of Intermediate Filaments in Vesicular Traffic

    Directory of Open Access Journals (Sweden)

    Azzurra Margiotta

    2016-04-01

    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.

  16. Calcium depletion in rabbit myocardium. Calcium paradox protection by hypothermia and cation substitution.

    Science.gov (United States)

    Rich, T L; Langer, G A

    1982-08-01

    The purpose of this study was to define further the basis of control of myocardial membrane permeability by further examination of the "calcium paradox." To this end, the protective effect of hypothermia and addition of micromolar amounts of divalent cations during the Ca-free perfusion period were studied. Damage during Ca++ repletion to the isolated arterially perfused, interventricular rabbit septum was assessed by contracture development, loss of developed tension, and loss of 42K and creatine kinase. Progressive hypothermia prolongs the time of Ca-free perfusion needed to cause similar 42K, creatine kinase and developed tension losses upon Ca++ repletion. Complete protection against the Ca-paradox after 30-60 minutes Ca-free perfusion is seen at 18 degree C. The inclusion of 50 microM Ca++ during 30 minutes "Ca-free" perfusion also provides complete protection during Ca++ repletion i.e., there was full mechanical recovery with no 42K or creatine kinase loss. Other divalent cations perfused in 50 microM concentrations during the Ca-free period exhibited variable ability to protect when Ca++ was reperfused. The order of effectiveness (Ca++ greater than Cd++ greater than Mn++ greater than Co++ greater than Mg++) was related to the crystal ionic radius, with those cations whose radii are closest to that of Ca++ (0.99 A) exerting the greatest protective effect. The cation sequence for effectiveness in Ca-paradox protection is the same sequence for potency of excitation-contraction uncoupling. The mechanism of hypothermic protection is likely a phase transition in the membrane lipids (from a more liquid to a less liquid state) which stabilizes membrane structure and preserves Ca++ permeability characteristics during the Ca-free period. The mechanism of protection via cation addition is perhaps a cation's ability to substitute for Ca++ (dependent on unhydrated crystal ionic radius) at critical sarcolemmal binding sites to preserve control of Ca++ permability during

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

    Directory of Open Access Journals (Sweden)

    Zou Weiwei

    2009-01-01

    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.

  18. Fluconazole affects the alkali-metal-cation homeostasis and susceptibility to cationic toxic compounds of Candida glabrata.

    Science.gov (United States)

    Elicharova, Hana; Sychrova, Hana

    2014-08-01

    Candida glabrata is a salt-tolerant and fluconazole (FLC)-resistant yeast species. Here, we analyse the contribution of plasma-membrane alkali-metal-cation exporters, a cation/proton antiporter and a cation ATPase to cation homeostasis and the maintenance of membrane potential (ΔΨ). Using a series of single and double mutants lacking CNH1 and/or ENA1 genes we show that the inability to export potassium and toxic alkali-metal cations leads to a slight hyperpolarization of the plasma membrane of C. glabrata cells; this hyperpolarization drives more cations into the cells and affects cation homeostasis. Surprisingly, a much higher hyperpolarization of C. glabrata plasma membrane was produced by incubating cells with subinhibitory concentrations of FLC. FLC treatment resulted in a substantially increased sensitivity of cells to various cationic drugs and toxic cations that are driven into the cell by negative-inside plasma-membrane potential. The effect of the combination of FLC plus cationic drug treatment was enhanced by the malfunction of alkali-metal-cation transporters that contribute to the regulation of membrane potential and cation homeostasis. In summary, we show that the combination of subinhibitory concentrations of FLC and cationic drugs strongly affects the growth of C. glabrata cells. © 2014 The Authors.

  19. Rapid and annealing-free self-assembly of DNA building blocks for 3D hydrogel chaperoned by cationic comb-type copolymers.

    Science.gov (United States)

    Zhang, Zheng; Wu, Yuyang; Yu, Feng; Niu, Chaoqun; Du, Zhi; Chen, Yong; Du, Jie

    2017-10-01

    The construction and self-assembly of DNA building blocks are the foundation of bottom-up development of three-dimensional DNA nanostructures or hydrogels. However, most self-assembly from DNA components is impeded by the mishybridized intermediates or the thermodynamic instability. To enable rapid production of complicated DNA objects with high yields no need for annealing process, herein different DNA building blocks (Y-shaped, L- and L'-shaped units) were assembled in presence of a cationic comb-type copolymer, poly (L-lysine)-graft-dextran (PLL-g-Dex), under physiological conditions. The results demonstrated that PLL-g-Dex not only significantly promoted the self-assembly of DNA blocks with high efficiency, but also stabilized the assembled multi-level structures especially for promoting the complicated 3D DNA hydrogel formation. This study develops a novel strategy for rapid and high-yield production of DNA hydrogel even derived from instable building blocks at relatively low DNA concentrations, which would endow DNA nanotechnology for more practical applications.

  20. ESL intermediate/advanced writing

    CERN Document Server

    Munoz Page, Mary Ellen; Jaskiewicz, Mary

    2011-01-01

    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

  1. Photonuclear reactions at intermediate energy

    International Nuclear Information System (INIS)

    Koch, J.H.

    1982-01-01

    The dominant feature of photonuclear reactions at intermediate energies is the excitation of the δ resonance and one can therefore use such reactions to study the dynamics of δ propagation in a nucleus. Following an introductory section the author comments on photoabsorption on a single nucleon in Section II. A review of the δ-n Greens function and of the photonuclear amplitude is given in Section III. Results for photoabsorption on 4 He are shown in Section IV and compared with the data. Coherent π 0 photoproduction is discussed in Section V and calculations for 12 C are compared to recent measurements. (Auth.)

  2. Pelamis WEC - intermediate scale demonstration

    Energy Technology Data Exchange (ETDEWEB)

    Yemm, R.

    2003-07-01

    This report describes the successful building and commissioning of an intermediate 1/7th scale model of the Pelamis Wave Energy Converter (WEC) and its testing in the wave climate of the Firth of Forth. Details are given of the design of the semi-submerged articulated structure of cylindrical elements linked by hinged joints. The specific programme objectives and conclusions, development issues addressed, and key remaining risks are discussed along with development milestones to be passed before the Pelamis WEC is ready for full-scale prototype testing.

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

    KAUST Repository

    Casu, Alberto; Genovese, Alessandro; Manna, Liberato; Longo, Paolo; Buha, Joka; Botton, Gianluigi A.; Lazar, Sorin; Kahaly, M. Upadhyay; Schwingenschlö gl, Udo; Prato, Mirko; Li, Hongbo; Ghosh, Sandeep; Palazon, Francisco; De Donato, Francesco; Lentijo Mozo, Sergio; Zuddas, Efisio; Falqui, Andrea

    2016-01-01

    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.

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

    KAUST Repository

    Casu, Alberto

    2016-01-27

    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.

  5. Intermediality: Bridge to Critical Media Literacy.

    Science.gov (United States)

    Pailliotet, Ann Watts; Semali, Ladislaus; Rodenberg, Rita K.; Giles, Jackie K.; Macaul, Sherry L.

    2000-01-01

    Defines "intermediality" as the ability to critically read and write with and across varied symbol systems. Relates it to critical media literacy. Offers rationales for teaching critical media literacy in general, and intermedial instruction in particular. Identifies seven guiding intermedial elements: theory, texts, processes, contexts,…

  6. Selective alkylation by photogenerated aryl and vinyl cation

    NARCIS (Netherlands)

    Slegt, Micha

    2006-01-01

    Seven para-substituted phenyl cations and the parent phenyl cation were prepared from iodonium salt precursors. Product studies revealed remarkable chemoselectivity and regioselectivity that could be related to the spin multiplicity of the cations. Also an universal method to fingerprint singlet and

  7. Post-crisis financial intermediation

    Directory of Open Access Journals (Sweden)

    Ilie MIHAI

    2015-09-01

    Full Text Available The recent financial crisis that begun in 2007 in the US, which then swept around the world, has left deep scars on the already wrinkled face of the global economy. Some national and regional economies, which had money for expensive makeup, or created money[1], managed to blur or hide the scars left by the crisis, others are still facing difficulties in overcoming the effects of this. The rapacity of banks, their greed and risk ignorance, were the origin of the outbreak of the last major economic and financial crisis but unfortunately those who were responsible or, rather, irresponsible, paid little or nothing at all for the burden of their bad loan portfolio. This cost has been supported by the population, either directly by paying high interest and fees [Mihai I., 2007], or indirectly, through the use of public budgets to cover the losses of banks, most of which had private capital. In this context, we intend to examine the state of financial intermediation in Romania in the post-crisis period, and to primarily follow: (i The structure and evolution of the banking system; (ii Non-government credit situation; (iii The level of savings; (iiii Loan-deposit ratio; (v The degree of financial intermediation and disintegration phenomenon etc., and to articulate some conclusions and suggestions on the matters that have been explored.

  8. Intermediate-Mass Black Holes

    Science.gov (United States)

    Miller, M. Coleman; Colbert, E. J. M.

    2004-01-01

    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 (M~3 20 M⊙), which are produced by the core collapse of massive stars, and supermassive (M~106 1010 M⊙), 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 M~102 104 M⊙. 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 that will help clarify numerous outstanding questions about these objects.

  9. Association of alkali and alkaline earth metal cations with radical-anions of 9-fluorenone and 9.10-anthraquinone in dimethyl formamide medium

    International Nuclear Information System (INIS)

    Karpinets, A.P.; Bezuglyj, V.D.; Svetlichnaya, T.M.

    1988-01-01

    The polarographic method is used to estimate the stability of associates formed in dimethyl formamide by the products of one-electron reduction of 9-fluorenone and 9.10-anthraquinone with cations of alkali and alkali earth metals. It is shown that the strength of 9-fluorenone and 9.10-anthraquinone radical anion associates studied increases with cation charge increase and decrease of its crystallographic radius

  10. Ferrocene-based diradicals of imino nitroxide, nitronyl nitroxide and verdazyl, and their cations are possible SMM: A quantum chemical study

    Science.gov (United States)

    Pal, Arun K.; Datta, Sambhu N.

    2017-05-01

    Six diradicals designed from imino nitroxide, verdazyl and nitronyl nitroxide monoradicals coupled via the ferrocene moiety and six corresponding triradical cations are quantum chemically investigated. The transoid conformation is employed for considerations of general stability. All biradicals are found as very weakly and antiferromagnetically coupled. This agrees with experiment. The cations have strong antiferromagnetic spin-coupling. The charge and spin population distributions, spin alternation pattern, and the disjoint nature of SOMOs can be used to explain the nature and extent of magnetic interaction. Calculated EPR characteristics identify the neutral species as well as their cations as possible single molecule magnets.

  11. Radiation chemistry of aromatic dimer radical cations

    International Nuclear Information System (INIS)

    Okamoto, Kazumasa; Tagawa, Seiichi

    2009-01-01

    π-π Interactions of aromatic molecules are paid attention much in many fields, especially biology, chemistry, and applied physics, represented as protein, DNA, electron donor-accepter complexes, charge transfers, and self assembly molecules. Aromatic molecules including benzene rings are the simplest case to study the π-π interactions. To interpret the charge resonance (CR) structure in the dimer radical cations, spectroscopic and ESR methods have been carried out. The spectroscopic study on the dimer radical ion of molecules with two chromophores would be profitable to identify the electronic and configurational properties. In this article, dynamics of the dimer radical cation of benzenes, polystyrenes, and resist polymers is described on the basis of direct observation of CR band by the nanosecond pulse radiolysis and low temperature γ-radiolysis methods. (author)

  12. Electronic spectrum of 9-methylanthracenium radical cation

    Energy Technology Data Exchange (ETDEWEB)

    O’Connor, Gerard D.; Schmidt, Timothy W., E-mail: timothy.schmidt@unsw.edu.au [School of Chemistry, UNSW Sydney, New South Wales 2052 (Australia); Sanelli, Julian A.; Dryza, Vik; Bieske, Evan J. [School of Chemistry, The University of Melbourne, Victoria 3010 (Australia)

    2016-04-21

    The predissociation spectrum of the cold, argon-tagged, 9-methylanthracenium radical cation is reported from 8000 cm{sup −1} to 44 500 cm{sup −1}. The reported spectrum contains bands corresponding to at least eight electronic transitions ranging from the near infrared to the ultraviolet. These electronic transitions are assigned through comparison with ab initio energies and intensities. The infrared D{sub 1}←D{sub 0} transitions exhibit significant vibronic activity, which is assigned through comparison with TD-B3LYP excited state frequencies and intensities, as well as modelled vibronic interactions. Dissociation of 9-methylanthracenium is also observed at high visible-photon energies, resulting in the loss of either CH{sub 2} or CH{sub 3}. The relevance of these spectra, and the spectra of other polycyclic aromatic hydrocarbon radical cations, to the largely unassigned diffuse interstellar bands, is discussed.

  13. Photodissociation of spatially aligned acetaldehyde cations.

    Science.gov (United States)

    Lee, Suk Kyoung; Silva, Ruchira; Kim, Myung Hwa; Shen, Lei; Suits, Arthur G

    2007-07-26

    Photofragment translational energy and angular distributions are reported for the photodissociation of acetaldehyde cations in the wavelength range 354-363 nm obtained using the DC slice ion imaging technique. Vibrationally selected parent ions were produced by 2+1 resonance-enhanced multiphoton ionization (REMPI) via the 3sCH3CO+, and CH4+. The angular distributions reveal that all product channels have a predominantly parallel recoil anisotropy although the lower beta2 parameter of CH3CO+ indicates the concomitant presence of a perpendicular component. Furthermore, the distinct angular distribution of the CH3CO+ fragments shows a large value of the higher order Legendre polynomial term, providing evidence that acetaldehyde cations are spatially aligned during the ionization process.

  14. Mechanism of adsorption of cations onto rocks

    International Nuclear Information System (INIS)

    Kitamura, Akira; Yamamoto, Tadashi; Fujiwara, Kenso; Nishikawa, Sataro; Moriyama, Hirotake

    1999-01-01

    Adsorption behavior of cations onto granite was investigated. The distribution coefficient (K d ) of Sr 2+ and Ba 2+ onto granite was determined in the solution of which pH was ranged from 3.5 to 11.3 and ionic strength was set at 10 -2 and 10 -1 . The K d values were found to increase with increasing pH and with deceasing ionic strength. The obtained data were successfully analyzed by applying an electrical double layer model. The optimum parameter values of the double layer electrostatics and adsorption reactions were obtained, and the mechanism of adsorption of cations onto granite was discussed. Feldspar was found to play an important role in their adsorption. (author)

  15. Regulation of Cation Balance in Saccharomyces cerevisiae

    Science.gov (United States)

    Cyert, Martha S.; Philpott, Caroline C.

    2013-01-01

    All living organisms require nutrient minerals for growth and have developed mechanisms to acquire, utilize, and store nutrient minerals effectively. In the aqueous cellular environment, these elements exist as charged ions that, together with protons and hydroxide ions, facilitate biochemical reactions and establish the electrochemical gradients across membranes that drive cellular processes such as transport and ATP synthesis. Metal ions serve as essential enzyme cofactors and perform both structural and signaling roles within cells. However, because these ions can also be toxic, cells have developed sophisticated homeostatic mechanisms to regulate their levels and avoid toxicity. Studies in Saccharomyces cerevisiae have characterized many of the gene products and processes responsible for acquiring, utilizing, storing, and regulating levels of these ions. Findings in this model organism have often allowed the corresponding machinery in humans to be identified and have provided insights into diseases that result from defects in ion homeostasis. This review summarizes our current understanding of how cation balance is achieved and modulated in baker’s yeast. Control of intracellular pH is discussed, as well as uptake, storage, and efflux mechanisms for the alkali metal cations, Na+ and K+, the divalent cations, Ca2+ and Mg2+, and the trace metal ions, Fe2+, Zn2+, Cu2+, and Mn2+. Signal transduction pathways that are regulated by pH and Ca2+ are reviewed, as well as the mechanisms that allow cells to maintain appropriate intracellular cation concentrations when challenged by extreme conditions, i.e., either limited availability or toxic levels in the environment. PMID:23463800

  16. Determination of the vildagliptin intermediate enantiomer by chiralce-columns

    Directory of Open Access Journals (Sweden)

    Weina LI

    2017-06-01

    Full Text Available In order to establish a NP-HPLC method for the determination of enantiomer in vildagliptin intermediate, the determination is carried out on the column of ChiralpakAD-H(250 mm×4.6 mm, 5 μm, with the mobile phase of n-hexane, ethanol and methanol(volume ratio of 65∶25∶10)at flow rate of 0.8 mL/min. The sample volume is 10 μL, the wavelength is 210 nm and the column temperature is 35 ℃. The result shows that the vildagliptin intermediate and its enantiomer could be well separated and detected effectively; blank solvent doesn't interfere with the enantiomer assaying; the detection limit is 27 ng/mL and the quantification limit is 81 ng/mL; in repetitive test, the RSD of enantiomer assaying of samples are no more than 2.0%; in stability test, the RSD are no more than 2.0% in 12 h; the vildagliptin intermediate and its enantiomer could be well separated in the test of durability with all RSDs below 2.0%. The method is simple, reliable, accurate and durable, and can be used for determination of enantiomer in vildagliptin intermediate.

  17. Reducible cationic lipids for gene transfer.

    Science.gov (United States)

    Wetzer, B; Byk, G; Frederic, M; Airiau, M; Blanche, F; Pitard, B; Scherman, D

    2001-01-01

    One of the main challenges of gene therapy remains the increase of gene delivery into eukaryotic cells. We tested whether intracellular DNA release, an essential step for gene transfer, could be facilitated by using reducible cationic DNA-delivery vectors. For this purpose, plasmid DNA was complexed with cationic lipids bearing a disulphide bond. This reduction-sensitive linker is expected to be reduced and cleaved in the reducing milieu of the cytoplasm, thus potentially improving DNA release and consequently transfection. The DNA--disulphide-lipid complexation was monitored by ethidium bromide exclusion, and the size of complexes was determined by dynamic light scattering. It was found that the reduction kinetics of disulphide groups in DNA--lipid complexes depended on the position of the disulphide linker within the lipid molecule. Furthermore, the internal structure of DNA--lipid particles was examined by small-angle X-ray scattering before and after lipid reduction. DNA release from lipid complexes was observed after the reduction of disulphide bonds of several lipids. Cell-transfection experiments suggested that complexes formed with selected reducible lipids resulted in up to 1000-fold higher reporter-gene activity, when compared with their analogues without disulphide bonds. In conclusion, reduction-sensitive groups introduced into cationic lipid backbones potentially allow enhanced DNA release from DNA--lipid complexes after intracellular reduction and represent a tool for improved vectorization. PMID:11389682

  18. Metal fluoride complexes of Na,K-ATPase: characterization of fluoride-stabilized phosphoenzyme analogues and their interaction with cardiotonic steroids.

    Science.gov (United States)

    Cornelius, Flemming; Mahmmoud, Yasser A; Toyoshima, Chikashi

    2011-08-26

    The Na,K-ATPase belongs to the P-type ATPase family of primary active cation pumps. Metal fluorides like magnesium-, beryllium-, and aluminum fluoride act as phosphate analogues and inhibit P-type ATPases by interacting with the phosphorylation site, stabilizing conformations that are analogous to specific phosphoenzyme intermediates. Cardiotonic steroids like ouabain used in the treatment of congestive heart failure and arrhythmias specifically inhibit the Na,K-ATPase, and the detailed structure of the highly conserved binding site has recently been described by the crystal structure of the shark Na,K-ATPase in a state analogous to E2·2K(+)·P(i) with ouabain bound with apparently low affinity (1). In the present work inhibition, and subsequent reactivation by high Na(+), after treatment of shark Na,K-ATPase with various metal fluorides are characterized. Half-maximal inhibition of Na,K-ATPase activity by metal fluorides is in the micromolar range. The binding of cardiotonic steroids to the metal fluoride-stabilized enzyme forms was investigated using the fluorescent ouabain derivative 9-anthroyl ouabain and compared with binding to phosphorylated enzyme. The fastest binding was to the Be-fluoride stabilized enzyme suggesting a preformed ouabain binding cavity, in accord with results for Ca-ATPase where Be-fluoride stabilizes the E2-P ground state with an open luminal ion access pathway, which in Na,K-ATPase could be a passage for ouabain. The Be-fluoride stabilized enzyme conformation closely resembles the E2-P ground state according to proteinase K cleavage. Ouabain, but not its aglycone ouabagenin, prevented reactivation of this metal fluoride form by high Na(+) demonstrating the pivotal role of the sugar moiety in closing the extracellular cation pathway.

  19. How Cations Can Assist DNase I in DNA Binding and Hydrolysis

    Science.gov (United States)

    Guéroult, Marc; Picot, Daniel; Abi-Ghanem, Joséphine; Hartmann, Brigitte; Baaden, Marc

    2010-01-01

    DNase I requires Ca2+ and Mg2+ for hydrolyzing double-stranded DNA. However, the number and the location of DNase I ion-binding sites remain unclear, as well as the role of these counter-ions. Using molecular dynamics simulations, we show that bovine pancreatic (bp) DNase I contains four ion-binding pockets. Two of them strongly bind Ca2+ while the other two sites coordinate Mg2+. These theoretical results are strongly supported by revisiting crystallographic structures that contain bpDNase I. One Ca2+ stabilizes the functional DNase I structure. The presence of Mg2+ in close vicinity to the catalytic pocket of bpDNase I reinforces the idea of a cation-assisted hydrolytic mechanism. Importantly, Poisson-Boltzmann-type electrostatic potential calculations demonstrate that the divalent cations collectively control the electrostatic fit between bpDNase I and DNA. These results improve our understanding of the essential role of cations in the biological function of bpDNase I. The high degree of conservation of the amino acids involved in the identified cation-binding sites across DNase I and DNase I-like proteins from various species suggests that our findings generally apply to all DNase I-DNA interactions. PMID:21124947

  20. Anchoring cationic amphiphiles for nucleotide delivery: significance of DNA release from cationic liposomes for transfection.

    Science.gov (United States)

    Hirashima, Naohide; Minatani, Kazuhiro; Hattori, Yoshifumi; Ohwada, Tomohiko; Nakanishi, Mamoru

    2007-06-01

    We have designed and synthesized lithocholic acid-based cationic amphiphile molecules as components of cationic liposomes for gene transfection (lipofection). To study the relationship between the molecular structures of those amphiphilic molecules, particularly the extended hydrophobic appendant (anchor) at the 3-hydroxyl group, and transfection efficiency, we synthesized several lithocholic and isolithocholic acid derivatives, and examined their transfection efficiency. We also compared the physico-chemical properties of cationic liposomes prepared from these derivatives. We found that isolithocholic acid derivatives exhibit higher transfection efficiency than the corresponding lithocholic acid derivatives. This result indicates that the orientation and extension of hydrophobic regions influence the gene transfection process. Isolithocholic acid derivatives showed a high ability to encapsulate DNA in a compact liposome-DNA complex and to protect it from enzymatic degradation. Isolithocholic acid derivatives also facilitated the release of DNA from the liposome-DNA complex, which is a crucial step for DNA entry into the nucleus. Our results show that the transfection efficiency is directly influenced by the ability of the liposome complex to release DNA, rather than by the DNA-encapsulating ability. Molecular modeling revealed that isolithocholic acid derivatives take relatively extended conformations, while the lithocholic acid derivatives take folded structures. Thus, the efficiency of release of DNA from cationic liposomes in the cytoplasm, which contributes to high transfection efficiency, appears to be dependent upon the molecular shape of the cationic amphiphiles.

  1. (Cationic + nonionic) mixed surfactant aggregates for solubilisation of curcumin

    International Nuclear Information System (INIS)

    Kumar, Arun; Kaur, Gurpreet; Kansal, S.K.; Chaudhary, G.R.; Mehta, S.K.

    2016-01-01

    Highlights: • Critical micelle concentration of mixed surfactant has been measured. • Aqueous solubility and alkaline stability of curcumin has been significantly improved. • Location of curcumin within micelles has been evaluated. • Scavenging activity of curcumin has been improved. • Non-intercalative binding with ct-DNA has been observed. - Abstract: Curcumin is a potential drug for variety of diseases. Major limitations of curcumin are low water solubility, rapid hydrolytic degradation in alkaline medium and poor bioavailability. To overcome these limitations, highly potential mixed micellar system has been prepared. In order to reduce inter ionic repulsion and precipitation of surfactants, (cationic + non-ionic) mixed system have been chosen that directly influence its applicability. Hydrophobic chain of non-ionic surfactant significantly influences the cmc of mixed surfactant system as indicated by fluorescence and conductivity data. UV–visible spectroscopy analyses show that solubility, stability and antioxidant property of the curcumin is remarkably improved depending on cmc and aggregation number (N_a_g_g) of mixed surfactants, where N_a_g_g plays crucial role. Generally, curcumin undergoes complete degradation in slight basic medium, but stability has been maintained up to 8 h at pH-13 using formulated mixed micelles (only (20 to 25)% degraded). Location of curcumin which is monitored using emission spectroscopy, fluorescence quenching and "1H NMR spectroscopy techniques play the most important role. Observed results show that the major population of curcumin is located at the polar region and some are in hydrophobic region of the mixed micelles. To ensure the effect of mixed surfactants and curcumin loaded mixed surfactants on DNA, the interaction parameter indicates non-interclative interactions.

  2. Comparative analysis of cation/proton antiporter superfamily in plants.

    Science.gov (United States)

    Ye, Chu-Yu; Yang, Xiaohan; Xia, Xinli; Yin, Weilun

    2013-06-01

    The cation/proton antiporter superfamily is associated with the transport of monovalent cations across membranes. This superfamily was annotated in the Arabidopsis genome and some members were functionally characterized. In the present study, a systematic analysis of the cation/proton antiporter genes in diverse plant species was reported. We identified 240 cation/proton antiporters in alga, moss, and angiosperm. A phylogenetic tree was constructed showing these 240 members are separated into three families, i.e., Na(+)/H(+) exchangers, K(+) efflux antiporters, and cation/H(+) exchangers. Our analysis revealed that tandem and/or segmental duplications contribute to the expansion of cation/H(+) exchangers in the examined angiosperm species. Sliding window analysis of the nonsynonymous/synonymous substitution ratios showed some differences in the evolutionary fate of cation/proton antiporter paralogs. Furthermore, we identified over-represented motifs among these 240 proteins and found most motifs are family specific, demonstrating diverse evolution of the cation/proton antiporters among three families. In addition, we investigated the co-expressed genes of the cation/proton antiporters in Arabidopsis thaliana. The results showed some biological processes are enriched in the co-expressed genes, suggesting the cation/proton antiporters may be involved in these biological processes. Taken together, this study furthers our knowledge on cation/proton antiporters in plants. Copyright © 2013 Elsevier B.V. All rights reserved.

  3. The role of microorganisms in the mobility of radionuclides in soil II. Evaluation of siderophone-cation complex forming capacity

    International Nuclear Information System (INIS)

    Konyi, J.; Koska, P.; Berzsenyi, G.; Gazso, L.G.; Appanna, V.D.

    1997-01-01

    Siderophores are cation binding agents produced by microorganisms. They are specific for Fe(III) but may bind other cations, too. Gram positive bacteria, Gram negative bacteria, filamentous bacteria and fungi isolated from soil samples were examined for siderophore production using chrome-asurol agar plates. We found that 44.5% of the isolates are able to produce siderophores. Spectral analysis of the produced exudates shoved cobalt and zinc binding capacity. Adding of a strong complexing agent (EDDHA) does not influence the stability of the formed metal-complex. (authors)

  4. Radical cations of quadricyclane and norbornadiene in polar ZSM-5 matrices: Radical cation photochemical transformations without photons

    International Nuclear Information System (INIS)

    Barnabas, M.V.; Trifunac, A.D.

    1994-01-01

    Radical cations of quadricyclane (Q) and norbornadiene (NBD) are produced by γ-radiolysis in zeolites. In polar ZSM-5, only one radical cation is initially observed below 100K. Increasing the temperature above 200K gives rise to the cyclopentadiene radical cation. Higher temperatures (>360K) give rise to the cyclopenten-4-yl radical. The observation of cyclopentadiene radical cation implies the occurrence of the reverse Diels-Alder reaction. This is a thermally forbidden, photochemically allowed, process, which is made possible by the interaction of the polar zeolite matrix sites with parent NBD and Q radical cations

  5. Investigations on complexing cation exchangers and their use for trace analysis in natural waters

    International Nuclear Information System (INIS)

    Lang, H.

    1991-12-01

    The practicability of cation preconcentrations from natural waters by use of EDTrA- and 5-s-oxine- celluloses has been studied. For that purpose the protonation constants as well as the complexation capacities were determined by use of acid/base titrations. In additional titration experiments the complex stability constants for Cu 2+ , Mn 2+ , Co 2+ , Ni 2+ and Ca 2+ were determined examplarely. The interpretation of the experiments was performed using an optimised fit between calculated and experimentally determined pH-titration curves. Calculations have been done by the computer code 'MINEQL'. The determined stability constants are in the same order of magnitude as those given in literature for the water soluble complexes of EDTA, NTA or 5-s-oxine. The preconcentration of cations from natural water samples occurs in accordance with the theoretical predictions. Not ignorable disturbances appear for cations forming hydroxides or oxides in neutral or weakly acidic solutions. By use of radioactive isotopes for Sn 2+ , Zn 4+ and Nb 5+ it can be shown that those ions may form particles or colloids in natural waters. These particles will be filtered in the columns packed with the celluloses and can hardly be removed from there. (author)

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

    KAUST Repository

    Binetti, Enrico

    2015-10-27

    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.

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

    KAUST Repository

    Binetti, Enrico; Striccoli, Marinella; Sibillano, Teresa; Giannini, Cinzia; Brescia, Rosaria; Falqui, Andrea; Comparelli, Roberto; Corricelli, Michela; Tommasi, Raffaele; Agostiano, Angela; Curri, M Lucia

    2015-01-01

    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.

  8. Interaction of the univalent silver cation with [Gly6]-antamanide: Experimental and theoretical study

    Science.gov (United States)

    Makrlík, Emanuel; Böhm, Stanislav; Kvíčala, Jaroslav; Vaňura, Petr; Ruzza, Paolo

    2018-03-01

    On the basis of extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium Ag+(aq) + 1.Na+(nb) ⇄ 1.Ag+ (nb) + Na+(aq) occurring in the two-phase water - nitrobenzene system (1 = [Gly6]-antamanide; aq = aqueous phase, nb = nitrobenzene phase) was determined as log Kex (Ag+,1·Na+) = 1.5 ± 0.1. Further, the stability constant of the 1·Ag+ complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log βnb (1·Ag+) = 4.5 ± 0.2. Finally, by using quantum chemical DFT calculations, the most probable structure of the cationic complex species 1·Ag+ was derived. In the resulting complex, the "central" cation Ag+ is coordinated by four noncovalent interactions to the corresponding four carbonyl oxygen atoms of the parent ligand 1. Besides, the whole 1·Ag+ complex structure is stabilized by two intramolecular hydrogen bonds. The interaction energy of the considered 1·Ag+ complex was found to be -465.5 kJ/mol, confirming also the formation of this cationic species.

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

    Directory of Open Access Journals (Sweden)

    Pichai Aree

    2008-05-01

    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.

  10. Radiolysis studies on reactive intermediates

    International Nuclear Information System (INIS)

    Kevan, L.

    1977-11-01

    A more quantitative characterization of the structure and reaction mechanism of solvated electrons produced by high energy chemistry was developed. Neutral atoms may undergo solvation in polar media to cause significant geometrical rearrangement. The geometrical arrangement of six OH bond oriented water molecules around a localized electron is the preferred geometry in frozen aqueous systems even at low solute ion concentration. The energy level structure of electrons in polar aqueous and alcoholic glasses was systematized from a comparison of photoconductivity and optical spectra. Experimental and theoretical evidence on electron solvation was evaluated to suggest the dominance of first solvation shell orientation in the solvation process. A laser photolysis study as a function of temperature suggests that electron solvation in ethanol glass occurs by a hindered molecular reorientation mechanism. In mixed polar and nonpolar glassy matrices it was shown that the electron is first solvated in the nonpolar matrix and is later transformed to a more stable species surrounded by the polar molecules. It was found that the spin lattice relaxation of solvated electrons is dominated by a new mechanism characteristic of disordered matrices which involves relaxation by tunneling modes in the matrix. The noninteracting spin packet model of electron spin resonance lines was shown to apply to solvated electrons in deuterated matrices but not in protiated matrices. A new type of recombination fluorescence experiment was devised which allows easy distinction between tunnelling and diffusive recombination mechanisms between solvate electrons and cations. Several theoretical studies have helped to delimit the applicability of an electron tunneling mechanism to solvated electron reactions. Electron spin echospectrometry was used to demonstrate that silver atoms undergo dramatic solvation and desolvation changes in frozen aqueous systems

  11. Cationic niosomes an effective gene carrier composed of novel spermine-derivative cationic lipids: effect of central core structures.

    Science.gov (United States)

    Opanasopit, Praneet; Leksantikul, Lalita; Niyomtham, Nattisa; Rojanarata, Theerasak; Ngawhirunpat, Tanasait; Yingyongnarongkul, Boon-Ek

    2017-05-01

    Cationic niosomes formulated from Span 20, cholesterol (Chol) and novel spermine-based cationic lipids of multiple central core structures (di(oxyethyl)amino, di(oxyethyl)amino carboxy, 3-amino-1,2-dioxypropyl and 2-amino-1,3-dioxypropyl) were successfully prepared for improving transfection efficiency in vitro. The niosomes composed of spermine cationic lipid with central core structure of di(oxyethyl)amino revealed the highest gene transfection efficiency. To investigate the factors affecting gene transfection and cell viability including differences in the central core structures of cationic lipids, the composition of vesicles, molar ratio of cationic lipids in formulations and the weight ratio of niosomes to DNA. Cationic niosomes composed of nonionic surfactants (Span20), cholesterol and spermine-based cationic lipids of multiple central core structures were formulated. Gene transfection and cell viability were evaluated on a human cervical carcinoma cell line (HeLa cells) using pDNA encoding green fluorescent protein (pEGFP-C2). The morphology, size and charge were also characterized. High transfection efficiency was obtained from cationic niosomes composed of Span20:Chol:cationic lipid at the molar ratio of 2.5:2.5:0.5 mM. Cationic lipids with di(oxyethyl)amino as a central core structure exhibited highest transfection efficiency. In addition, there was also no serum effect on transfection efficiency. These novel cationic niosomes may constitute a good alternative carrier for gene transfection.

  12. Epitope mapping of imidazolium cations in ionic liquid-protein interactions unveils the balance between hydrophobicity and electrostatics towards protein destabilisation.

    Science.gov (United States)

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

    2014-11-14

    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).

  13. RHIZOME AND DISCOURSE OF INTERMEDIALITY

    Directory of Open Access Journals (Sweden)

    Л Н Синельникова

    2017-12-01

    Full Text Available Rhizomaticity is a strategy and a regularity of text creation in a lot of modern commu-nicative discourse practices. What remains urgent is the problem of the systematic interdisciplinary de-scription of texts whose structure and language qualities are determined by the signs of the rhizome - a concept of post-modern philosophy introduced into the scientific field by the French philosopher Gilles Deleuze and the psychotherapist Félix Guattari (Deleuze, Guattari 1996. The rhizome (Fr. rhizome - rootstock, tuber, bulb, mycelium possesses the following qualities: it is non-linear, open and directed towards the unpredictability of discourse transformations through the possibilities of structure development in any direction; there is no centre or periphery in the rhizome, and any discourse element can become ‘a vital structure’ for text-creation. The rhizome does not have non-intersecting boundaries; and in the space of the rhizomatic discourse environment, an increase of reality facets takes place, non-standard associative con-nections appear, multiplication effects are formed, which create new meanings. Rhizomaticity is the quality of texts being organised by the laws of rhizomatic logic (V.F. Sharkov 2007, by the terms of which ‘su-perposition’ of discourses can take place, a transition from one semiotic system to another. The article makes an attempt to correlate the qualities of the rhizome with the signs of the intermedia discourse, which is built on the semiotic interaction of different media. The moving lines of the rhizome, its ‘branch-ing’ qualities can be found in poetic texts, in the evaluating segments of political discourse, in advertising discourse, in internet communications, which represent rhizomorphic environments. An analysis of examples from these spheres has shown that the rhizomatic approach opens new facets of intermediality. The author uses the methods of discourse analysis to prove that the openness and non

  14. Biomimetic Cationic Nanoparticles Based on Silica: Optimizing Bilayer Deposition from Lipid Films

    Directory of Open Access Journals (Sweden)

    Rodrigo T. Ribeiro

    2017-10-01

    Full Text Available The optimization of bilayer coverage on particles is important for a variety of biomedical applications, such as drug, vaccine, and genetic material delivery. This work aims at optimizing the deposition of cationic bilayers on silica over a range of experimental conditions for the intervening medium and two different assemblies for the cationic lipid, namely, lipid films or pre-formed lipid bilayer fragments. The lipid adsorption on silica in situ over a range of added lipid concentrations was determined from elemental analysis of carbon, hydrogen, and nitrogen and related to the colloidal stability, sizing, zeta potential, and polydispersity of the silica/lipid nanoparticles. Superior bilayer deposition took place from lipid films, whereas adsorption from pre-formed bilayer fragments yielded limiting adsorption below the levels expected for bilayer adsorption.

  15. UV/Vis/NIR spectral properties of triarylamines and their corresponding radical cations

    International Nuclear Information System (INIS)

    Amthor, Stephan; Noller, Bastian; Lambert, Christoph

    2005-01-01

    The one-electron oxidation potential of 10 triarylamines 1-10 with all permutations of chloro-, methoxy- and methyl-substituents in the three para-positions were determined by cyclic voltammetry. The half wave potential E 1/2 (I) of the first oxidation wave correlates linearly with the number of chloro- and methoxy-substituents. A high long-term stability of the first oxidation wave for all triarylamines was observed by multi-cycle thin-layer measurements. AM1-CISD derived values of the absorption energies are in good agreement with the experiments but differ strongly for the oscillator strengths as well as for neutral compounds 1-10 and their corresponding mono radical cations. The small solvent dependence of the experimental UV/Vis spectra in CH 2 Cl 2 and MeCN reflects a minor charge transfer (CT) character of the electronic transitions of neutral and cationic compounds

  16. Small cationic antimicrobial peptidomimetics: emerging candidate for the development of potential anti-infective agents.

    Science.gov (United States)

    Lohan, Sandeep; Bisht, Gopal Singh

    2013-01-01

    Rapid increase in the emergence and spread of microbes resistant to conventionally used antibiotics has become a major threat to global health care. Antimicrobial peptides (AMPs) are considered as a potential source of novel antibiotics because of their numerous advantages such as broad-spectrum activity, lower tendency to induce resistance, immunomodulatory response and unique mode of action. However, AMPs have several drawbacks such as; susceptibility to protease degradation, toxicity and high costs of manufacturing. Therefore, extensive research efforts are underway to explore the therapeutic potential of these fascinating natural compounds. This review highlights the potential of small cationic antimicrobial peptidomimetics (SCAMPs; M.W. ≅ 700 Da) as new generation antibiotics. In particular, we focused on recently identified small active pharmacophore from bulky templates of native AMPs, β-peptides, and lipopeptides. In addition, various design strategies recently undertaken to improve the physicochemical properties (proteolytic stability & plasma protein binding) of small cationic peptides have also been discussed.

  17. Circular Cationic Compounds B3Rgn+ of Triangular Ion B3 Trapping Rare Gases

    Institute of Scientific and Technical Information of China (English)

    ZHANG Ruiwen; LI Anyong; LI Zhuozhe

    2017-01-01

    The circular cationic compounds B3Rgn+(n=1-3,Rg=He-Rn) formed by the electron-deficient aromatic ion B3+ trapping rare gases were studied theoretically.The formed B-Rg bond has large bonding energy in the range of 60--209 kJ/mol,its length is close to the stun of covalent radii of B and Rg,for Ar-Rn.The analyses based on the natural bond orbitals and electron density topology show that the B-Rg bonds for Ar-Rn have strong covalent character.The geometric structures,binding energy,bond nature and thermodynamic stability of the boron-rare gas compounds show that these species for Ar-Rn may be experimentally available.Several different theoretical studies have demonstrated that these triangular cations are aromatic.

  18. Role of Acetone in the Formation of Highly Dispersed Cationic Polystyrene Nanoparticles

    Directory of Open Access Journals (Sweden)

    Ernawati Lusi

    2017-03-01

    Full Text Available A modified emulsion polymerisation synthesis route for preparing highly dispersed cationic polystyrene (PS nanoparticles is reported. The combined use of 2,2′-azobis[2-(2-imidazolin- 2-ylpropane] di-hydrochloride (VA-044 as the initiator and acetone/water as the solvent medium afforded successful synthesis of cationic PS particles as small as 31 nm in diameter. A formation mechanism for the preparation of PS nanoparticles was proposed, whereby the occurrence of rapid acetone diffusion caused spontaneous rupture of emulsion droplets into smaller droplets. Additionally, acetone helped to reduce the surface tension and increase the solubility of styrene, thus inhibiting aggregation and coagulation among the particles. In contrast, VA-044 initiator could effectively regulate the stability of the PS nanoparticles including both the surface charge and size. Other reaction parameters i.e. VA-044 concentration and reaction time were examined to establish the optimum polymerisation conditions.

  19. Electrochemical insertion in solid media of alkali cations in carbonated host structures (polyacetylene, fullerene and graphite)

    International Nuclear Information System (INIS)

    Lemont, Sylvain

    1994-01-01

    This research thesis reports the investigation of electrochemical insertion of alkali cations in different host carbon containing structures (polyacetylene, fullerene, graphite). After a recall of the main characteristics of the three considered compounds, the author reports a bibliographical survey, describes the different compounds which can be used as solid electrolytes and explains the choice of the studied compounds with respect to their phase diagrams, ionic conductivity, electrochemical stability range. He describes the experimental methods, discusses the results obtained by intercalation of alkali cations (Li + , Na + , K + ) in polyacetylene. He discusses the electrochemical and structural results obtained on intercalation compounds of lithium and sodium ions in fullerene. The structures of several phases have been obtained by electron diffraction. Preliminary studies of electron energy loss spectrometry (EELS) are reported. The last part compares the results obtained on two types of graphite: pellets and spherules [fr

  20. (4+2) Cycloaddition reactions with inverse electron demand of nitrogen bearing, heteroaromatic cations

    International Nuclear Information System (INIS)

    Ritzberger-Baumgartner, W.

    1996-06-01

    Three cationic, heteroaromatic diene-systems (1, 2, 3, 4-tetramethoxycarbonyl-quinolizinium-tetrafluoroborate (M), 8, 9, 10, 11-tetrarnethoxycarbonylpyrido[2,1-a]-isoquinolinium-TFB and triazolo[1,5-b]isoquinolinium-TFBs) and a cationic, non-aromatic diene (2,5,5-trimethyl-3-oxo-1, 2, 4-triazolium-TFB) were synthesized. The dienes were employed successfully in cycloaddition reactions with a number ofconjugated dienophiles (including norbornene). The mechanism underlying these cycloaddition reactions was discussed in the theoretical section. At first quantumchemical calculations of the frontier orbital energies provided the proof, that the reactions followed the pattern of reactions with inverse electron demand. Calculation of the charge distribution and of the orbital coefficients led to the conclusion, that these reactions are mainly orbital controlled. Two mechanistic variants were in discussion. Either the reactions proceed in a concerted manner resembling the Diels-Alder reaction with inverse electron demand or in two distinct steps with the formation of a cationic intermediate following the attack of the heterodienes acting as weak electrophiles at the dienophiles being weak nucleophiles. Calculations of a possible transition state of these cycloaddition reactions revealed a pronounced preference for the formation of the bond between the logical reaction centers in the first step of a two-step reaction. However, experimental and theoretical findings led to the conviction, that cationic polar cycloaddition reactions proceed exactly along the crossroad between a concerted and a two-step mechanism and depending on the electrophilic strength of the diene and the nucleophilic strength of the dienophile these reactions show more characteristics of one of the two mechanistic possibilities. The high regioselectivity as well as the high stereoselectivity could be explained satisfactory with the help of the calculated orbital coefficients. (author)

  1. Aquatic toxicity and biodegradability of advanced cationic surfactant APA-22 compatible with the aquatic environment.

    Science.gov (United States)

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

    2008-01-01

    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.

  2. Complexes of natural carbohydrates with metal cations

    International Nuclear Information System (INIS)

    Alekseev, Yurii E; Garnovskii, Alexander D; Zhdanov, Yu A

    1998-01-01

    Data on the interaction of natural carbohydrates (mono-, oligo-, and poly-saccharides, amino sugars, and natural organic acids of carbohydrate origin) with metal cations are surveyed and described systematically. The structural diversity of carbohydrate metal complexes, caused by some specific features of carbohydrates as ligands, is demonstrated. The influence of complex formation on the chemical properties of carbohydrates is discussed. It is shown that the formation of metal complexes plays an important role in the configurational and conformational analysis of carbohydrates. The practical significance of the coordination interaction in the series of carbohydrate ligands is demonstrated. The bibliography includes 571 references.

  3. Complex Macromolecular Architectures by Living Cationic Polymerization

    KAUST Repository

    Alghamdi, Reem D.

    2015-05-01

    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

  4. Homogeneous cation exchange membrane by radiation grafting

    International Nuclear Information System (INIS)

    Kolhe, Shailesh M.; G, Agathian; Ashok Kumar

    2001-01-01

    Preparation of a strong cation exchange membrane by radiation grafting of styrene on to polyethylene (LDPE) film by mutual irradiation technique in the presence of air followed by sulfonation is described. The grafting has been carried out in the presence of air and without any additive. Low dose rate has been seen to facilitate the grafting. Further higher the grafting percentage more is the exchange capacity. The addition of a swelling agent during the sulfonation helped in achieving the high exchange capacity. The TGA-MASS analysis confirmed the grafting and the sulfonation. (author)

  5. Low- and intermediate-level waste management practices in Canada

    International Nuclear Information System (INIS)

    Charlesworth, D.H.

    1982-05-01

    Low- and intermediate-level wastes arise in Canada from the operation of nuclear power stations, nuclear research establishments, nuclear fuel and radioisotope production facilities, as well as from many medical, research and industrial organizations. Essentially all of the solid radioactive wastas are stored in a retrievable fashion at five waste management areas from which a portion is expected to be transferred to future disposal facilities. Waste processing for volume reduction and stabilization is becoming an increasingly important part of low-level waste management because of the advantages it provides for both interim storage currently, and permanent disposal in the future

  6. Influence of cationic lipid concentration on properties of lipid–polymer hybrid nanospheres for gene delivery

    Directory of Open Access Journals (Sweden)

    Bose RJC

    2015-09-01

    Full Text Available Rajendran JC Bose,1,2 Yoshie Arai,1 Jong Chan Ahn,1 Hansoo Park,2 Soo-Hong Lee11Department of Biomedical Science, College of Life Science, CHA University, Seongnam, 2Department of Integrative Engineering, Chung-Ang University, Seoul, South Korea Abstract: Nanoparticles have been widely used for nonviral gene delivery. Recently, cationic hybrid nanoparticles consisting of two different materials were suggested as a promising delivery vehicle. In this study, nanospheres with a poly(D,l-lactic-co-glycolic acid (PLGA core and cationic lipid shell were prepared, and the effect of cationic lipid concentrations on the properties of lipid polymer hybrid nanocarriers investigated. Lipid–polymer hybrid nanospheres (LPHNSs were fabricated by the emulsion-solvent evaporation method using different concentrations of cationic lipids and characterized for size, surface charge, stability, plasmid DNA-binding capacity, cytotoxicity, and transfection efficiency. All LPHNSs had narrow size distribution with positive surface charges (ζ-potential 52–60 mV, and showed excellent plasmid DNA-binding capacity. In vitro cytotoxicity measurements with HEK293T, HeLa, HaCaT, and HepG2 cells also showed that LPHNSs exhibited less cytotoxicity than conventional transfection agents, such as Lipofectamine and polyethyleneimine–PLGA. As cationic lipid concentrations increased, the particle size of LPHNSs decreased while their ζ-potential increased. In addition, the in vitro transfection efficiency of LPHNSs increased as lipid concentration increased. Keywords: core–shell hybrid nanospheres, lipid concentration, surface modification, low cytotoxicity, transfection efficiency

  7. Hydrogen Bonding and Stability of Hybrid Organic-Inorganic Perovskites

    KAUST Repository

    El-Mellouhi, Fedwa

    2016-09-08

    In the past few years, the efficiency of solar cells based on hybrid organic–inorganic perovskites has exceeded the level needed for commercialization. However, existing perovskites solar cells (PSCs) suffer from several intrinsic instabilities, which prevent them from reaching industrial maturity, and stabilizing PSCs has become a critically important problem. Here we propose to stabilize PSCs chemically by strengthening the interactions between the organic cation and inorganic anion of the perovskite framework. In particular, we show that replacing the methylammonium cation with alternative protonated cations allows an increase in the stability of the perovskite by forming strong hydrogen bonds with the halide anions. This interaction also provides opportunities for tuning the electronic states near the bandgap. These mechanisms should have a universal character in different hybrid organic–inorganic framework materials that are widely used.

  8. Hydrogen Bonding and Stability of Hybrid Organic-Inorganic Perovskites

    KAUST Repository

    El-Mellouhi, Fedwa; Marzouk, Asma; Bentria, El Tayeb; Rashkeev, Sergey N.; Kais, Sabre; Alharbi, Fahhad H.

    2016-01-01

    In the past few years, the efficiency of solar cells based on hybrid organic–inorganic perovskites has exceeded the level needed for commercialization. However, existing perovskites solar cells (PSCs) suffer from several intrinsic instabilities, which prevent them from reaching industrial maturity, and stabilizing PSCs has become a critically important problem. Here we propose to stabilize PSCs chemically by strengthening the interactions between the organic cation and inorganic anion of the perovskite framework. In particular, we show that replacing the methylammonium cation with alternative protonated cations allows an increase in the stability of the perovskite by forming strong hydrogen bonds with the halide anions. This interaction also provides opportunities for tuning the electronic states near the bandgap. These mechanisms should have a universal character in different hybrid organic–inorganic framework materials that are widely used.

  9. FINANCIAL INTERMEDIATION, ENTREPRENEURSHIP AND ECONOMIC GROWTH

    OpenAIRE

    Wenli Cheng

    2007-01-01

    This paper presents a simple general equilibrium model of financial intermediation, entrepreneurship and economic growth. In this model, the role of financial intermediation is to pool savings and to lend the pooled funds to an entrepreneur, who in turn invests the funds in a new production technology. The adoption of the new production technology improves individual real income. Thus financial intermediation promotes economic growth through affecting individuals’ saving behaviour and enabl...

  10. Biocatalytic Synthesis of Chiral Pharmaceutical Intermediates

    Directory of Open Access Journals (Sweden)

    Ramesh N. Patel

    2004-01-01

    Full Text Available 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 from both the pharmaceutical and agrochemical industries for the preparation of bulk drug substances and agricultural products. The enormous potential of microorganisms and enzymes for the transformation of synthetic chemicals with high chemo-, regio- and enantioselectivities has been demonstrated. In this article, biocatalytic processes are described for the synthesis of chiral pharmaceutical intermediates.

  11. Regularities of intermediate adsorption complex relaxation

    International Nuclear Information System (INIS)

    Manukova, L.A.

    1982-01-01

    The experimental data, characterizing the regularities of intermediate adsorption complex relaxation in the polycrystalline Mo-N 2 system at 77 K are given. The method of molecular beam has been used in the investigation. The analytical expressions of change regularity in the relaxation process of full and specific rates - of transition from intermediate state into ''non-reversible'', of desorption into the gas phase and accumUlation of the particles in the intermediate state are obtained

  12. Influence of the substitution of β-cyclodextrins by cationic groups on the complexation of organic anions

    International Nuclear Information System (INIS)

    Hbaieb, S.; Kalfat, R.; Chevalier, Y.; Amdouni, N.; Parrot-Lopez, H.

    2008-01-01

    The inclusion complexation of the organic anion, dansyl-acid, by cationic derivatives of β-cyclodextrin has been investigated. A series of cationic β-cyclodextrins with various positive charge has been synthesized by selective functionalization of the primary face of β-cyclodextrin with amino groups. The complexes were of the 1:1 stoichiometry; the stability constants (K 11 ) have been evaluated from UV-Vis measurements by application of the Benesi-Hildebrand equation. The presence of amino groups increased the complexation ability. β-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

  13. 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: Souhairabouchaira@yahoo.fr; 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: chevalier@lagep.univ-lyon1.fr; 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: helene.parrot@univ-lyon1.fr

    2008-07-01

    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.

  14. Experiments in intermediate energy physics

    International Nuclear Information System (INIS)

    Dehnhard, D.

    2003-01-01

    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

  15. Experiments in intermediate energy physics

    Energy Technology Data Exchange (ETDEWEB)

    Dehnhard, D.

    2003-02-28

    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.

  16. Research of thermal stability of ion exchangers

    International Nuclear Information System (INIS)

    Stuchlik, S.; Srnkova, J.

    1983-01-01

    Prior to the fixation of radioactive ion exchangers into bitumen these exchangers have to be dried. The resulting gaseous products may generate explosive mixtures. An analysis was made of the thermal stability of two types of ion exchangers, the cation exchanger KU-2-8 cS and the anion exchanger AV-17-8 cS which are used in the V-1 nuclear power plant at Jaslovske Bohunice. The thermal stability of the anion exchangers was monitored using gas chromatography at temperatures of 100, 120, 140, 160 and 180 degC and by measuring weight loss by kiln-drying at temperatures of 120, 140, 160 and 180 degC. The ion exchanger was heated for 6 hours and samples were taken continuously at one hour intervals. The thermal stability of the cation exchanger was monitored by measuring the weight loss. Gas chromatography showed the release of trimethylamine from the anion exchanger in direct dependence on temperature. The measurement of weight losses, however, only showed higher losses of released products which are explained by the release of other thermally unstable products. The analysis of the thermal stability of the cation exchanger showed the release of SO 2 and the weight loss (following correction for water content) was found only after the fourth hour of decomposition. The experiment showed that the drying of anion exchanger AV-17-8 cS may cause the formation of explosive mixtures. (J.P.)

  17. Cationic polymers in water treatment: Part 1: Treatability of water with cationic polymers

    Czech Academy of Sciences Publication Activity Database

    Polasek, P.; Mutl, Silvestr

    2002-01-01

    Roč. 28, č. 1 (2002), s. 69-82 ISSN 0378-4738 R&D Projects: GA AV ČR KSK2067107 Keywords : cationic polymers * treatability * water quality Subject RIV: BK - Fluid Dynamics Impact factor: 0.481, year: 2002

  18. Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism.

    Science.gov (United States)

    Boughlala, Zakaria; Fonseca Guerra, Célia; Bickelhaupt, F Matthias

    2016-06-01

    We have analyzed the structure and bonding of gas-phase Cl-X and [HCl-X](+) complexes for X(+)= H(+), CH3 (+), Li(+), and Na(+), using relativistic density functional theory (DFT). We wish to establish a quantitative trend in affinities of the anionic and neutral Lewis bases Cl(-) and HCl for the various cations. The Cl-X bond becomes longer and weaker along X(+) = H(+), CH3 (+), Li(+), and Na(+). Our main purpose is to understand the heterolytic bonding mechanism behind the intrinsic (i.e., in the absence of solvent) alkali metal cation affinities (AMCA) and how this compares with and differs from those of the proton affinity (PA) and methyl cation affinity (MCA). Our analyses are based on Kohn-Sham molecular orbital (KS-MO) theory in combination with a quantitative energy decomposition analysis (EDA) that pinpoints the importance of the different features in the bonding mechanism. Orbital overlap appears to play an important role in determining the trend in cation affinities.

  19. Sulfation and cation effects on the conformational properties of the glycan backbone of chondroitin sulfate disaccharides.

    Science.gov (United States)

    Faller, Christina E; Guvench, Olgun

    2015-05-21

    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 10 disaccharides (β1-3 vs β1-4 linkage × 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 information

  20. Cobalt 60 cation exchange with mexican clays

    International Nuclear Information System (INIS)

    Nava Galve, R.G.

    1993-01-01

    Mexican clays can be used to remove radioactive elements from contaminated aqueous solutions. Cation exchange experiments were performed with 60 Co radioactive solution. In the present work the effect of contact time on the sorption of Co 2+ was studied. The contact time in hydrated montmorillonite was from 5 to 120 minutes and in dehydrated montmorillonite 5 to 1400 minutes. The Co 2+ uptake value was, in hydrated montmorillonite, between 0.3 to 0.85 m eq/g and in dehydrated montmorillonite, between 0.6 to 1.40 m eq/g. The experiments were done in a pH 5.1 to 5.7 and normal conditions. XRD patterns were used to characterize the samples. The crystallinity was determined by X-ray Diffraction and it was maintained before and after the cation exchange. DTA thermo grams showed the temperatures of the lost humidity and crystallization water. Finally, was observed that dehydrated montmorillonite adsorb more cobalt than hydrated montmorillonite. (Author)

  1. Cationic antimicrobial peptides in penaeid shrimp.

    Science.gov (United States)

    Tassanakajon, Anchalee; Amparyup, Piti; Somboonwiwat, Kunlaya; Supungul, Premruethai

    2011-08-01

    Penaeid shrimp aquaculture has been consistently affected worldwide by devastating diseases that cause a severe loss in production. To fight a variety of harmful microbes in the surrounding environment, particularly at high densities (of which intensive farming represents an extreme example), shrimps have evolved and use a diverse array of antimicrobial peptides (AMPs) as part of an important first-line response of the host defense system. Cationic AMPs in penaeid shrimps composed of penaeidins, crustins, and anti-lipopolysaccharide factors are comprised of multiple classes or isoforms and possess antibacterial and antifungal activities against different strains of bacteria and fungi. Shrimp AMPs are primarily expressed in circulating hemocytes, which is the main site of the immune response, and hemocytes expressing AMPs probably migrate to infection sites to fight against pathogen invasion. Indeed, most AMPs are produced as early as the nauplii developmental stage to protect shrimp larvae from infections. In this review, we discuss the sequence diversity, expression, gene structure, and antimicrobial activities of cationic AMPs in penaeid shrimps. The information available on antimicrobial activities indicates that these shrimp AMPs have potential therapeutic applications in the control of disease problems in aquaculture.

  2. Cationic Antimicrobial Polymers and Their Assemblies

    Science.gov (United States)

    Carmona-Ribeiro, Ana Maria; de Melo Carrasco, Letícia Dias

    2013-01-01

    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. PMID:23665898

  3. Cationic Antimicrobial Polymers and Their Assemblies

    Directory of Open Access Journals (Sweden)

    Ana Maria Carmona-Ribeiro

    2013-05-01

    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.

  4. Basic exchangeable cations in Finnish mineral soils

    Directory of Open Access Journals (Sweden)

    Armi Kaila

    1972-09-01

    Full Text Available The content of exchangeable Ca, Mg, K and Na replaced by neutral ammonium acetate was determined in 470 samples of mineral soils from various parts of Finland, except from Lapland. The amount of all these cations tended to increase with an increase in the clay content, but variation within each textural class was large, and the ranges usually overlapped those of the other classes. The higher acidity of virgin surface soils was connected with a lower average degree of saturation by Ca as compared with the corresponding textural classes of cultivated soils. No significant difference in the respective contents of other cations was detected. The samples of various textural groups from deeper layers were usually poorer in exchangeable Ca and K than the corresponding groups of plough layer. The mean content of exchangeable Mg was equal or even higher in the samples from deeper layers than in the samples from plough layer, except in the group of sand soils. The percentage of Mg of the effective CEC increased, as an average, from 9 in the sand and fine sand soils of plough layer to 30 in the heavy clay soils; in the heavy clay soils from deeper layers its mean value was 38 ± 4 %. In the samples of plough layer, the mean ratio of Ca to Mg in sand and fine sand soils was about 9, in silt and loam soils about 6, in the coarser clay soils about 4, and in heavy clay about 2.

  5. Radiochemical study of isomerization of free butyl cations

    International Nuclear Information System (INIS)

    Sinotova, E.N.; Nefedov, V.D.; Skorokhodov, S.S.; Arkhipov, Yu.M.

    1987-01-01

    Ion-molecular reactions of free butyl cations, generated by nuclear chemical method, with carbon monoxide containing small quantities of ethanol vapors are studied. Carbon monoxide was used to fix instable butyl cations in the form of corresponding acyl ions. Ester of α-methyl-butyric acid appears to be the only product of free butyl cation interaction with carbon monoxide in the presence of ethanol vapors. That means, that up to the moment of butyl cation reaction with carbon monoxide, the primary butyl cations are almost completely isomerized into secondary in agreement with results of previous investigations. This allows one to study free butyl cation isomerization process according to ion-molecular reaction product isomeric composition

  6. Nuclear structure at intermediate energies

    International Nuclear Information System (INIS)

    Bonner, B.E.; Mutchler, G.S.

    1991-01-01

    The theme that unites the sometimes seemingly disparate experiments undertaken by the Bonner Lab Medium Energy Group is a determination to understand in detail the many facets and manifestations of the strong interaction, that which is now referred to as nonperturbative QCD. Whether we are investigating the question of just what does carry the spin of baryons, or the extent of the validity of the SU(6) wavefunctions for the excited hyperons (as will be measured in their radiative decays in our CEBAF experiment), or questions associated with the formation of a new state of matter predicted by QCD (the subject of our BNL experiments E810, E854, as well as our approved experiment at RHIC), -- all these projects share this common goal. Our other experiments represent different approaches to the same broad undertaking. LAMPF E1097 will provide definitive answers to the question of the spin dependence of the inelastic channel of pion production in the n-p interaction. FNAL E683 may well open a new field of investigation in nuclear physics: that of just how quarks and gluons interact with nuclear matter as they transverse nuclei of different sizes. In most all of the experiments mentioned above, the Bonner Lab Group is playing major leadership roles as well as doing a big fraction of the hard work that such experiments require. We use many of the facilities that are unavailable to the intermediate energy physics community and we use our expertise to design and fabricate the detectors and instrumentation that are required to perform the measurements which we decide to do

  7. Parturient hypocalcemia in jersey cows fed alfalfa haylage-based diets with different cation to anion ratios.

    Science.gov (United States)

    Gaynor, P J; Mueller, F J; Miller, J K; Ramsey, N; Goff, J P; Horst, R L

    1989-10-01

    Jersey cows were fed three alfalfa haylage-based diets with different cation-anion balances beginning 6 wk preceding third or later calving and ending 24 to 36 h postpartum. Sodium and Cl as percentages of dietary DM were .08 and 1.66 in diet 1 (anionic, 5 cows), .44 and .91 in diet 2 (intermediate, 6 cows), and 1.60 and .34 in diet 3 (cationic, 6 cows). Cation-anion balances were 22, 60, and 126 meq/100 g DM; Ca:P ratios averaged 4:1. Cows fed diet 1 in comparison with cows fed diets 2 or 3 over 6 wk had similar concentrations of Ca, P, and Na but higher concentrations of Mg and K in plasma and higher urinary excretions of Ca and Mg. Concentrations of 1,25-dihydroxyvitamin D 3 d before parturition were higher in cows fed diet 1 than in cows fed diets 2 or 3. Within 36 h after calving, mean concentrations of Ca in plasma (mg/dl, range) of cows fed diets 1 to 3, respectively, were 7 (8.7 to 6.2), 6.5 (7.8 to 3.9), and 6.3 (7.8 to 3.8). Number of cases of clinical milk fever by diet were 0 of 5, 2 of 6, and 1 of 6 cows. Alteration of dietary cation-anion balance by addition of Cl may effectively reduce incidence and severity of parturient hypocalcemia.

  8. Designing structural features of novel benznidazole-loaded cationic nanoparticles for inducing slow drug release and improvement of biological efficacy.

    Science.gov (United States)

    Dos Santos-Silva, Alaine M; de Caland, Lilia B; de S L Oliveira, Ana Luíza C; de Araújo-Júnior, Raimundo F; Fernandes-Pedrosa, Matheus F; Cornélio, Alianda Maira; da Silva-Júnior, Arnóbio A

    2017-09-01

    Several polymers have been investigated for producing cationic nanocarriers due to their ability to cross biological barriers. Polycations such as copolymers of polymethylmethacrylate are highlighted due to their biocompatibility and low toxicity. The purpose of this study was to produce small and narrow-sized cationic nanoparticles able to overcome cell membranes and improve the biological activity of benznidazole (BNZ) in normal and cancer cells. The effect of composition and procedure parameters of the used emulsification-solvent evaporation method were controlled for this purpose. The experimental approach included particle size, polydispersity index, zeta potential, atomic force microscopy (AFM), attenuated total reflectance Fourier transforms infrared spectroscopy (ATR- FTIR), drug loading efficiency, and physical stability assays. Spherical and stable (over six weeks) sub 150nm cationic nanoparticles were optimized, with the encapsulation efficiency >80%. The used drug/copolymer ratio modulated the slow drug release, which was adjusted by the parabolic diffusion mathematical model. In addition, the ability of the cationic nanoparticles improve the BNZ uptake in the normal kidney cells (HEK 293) and the human colorectal cancer cells (HT 29) demonstrate that this novel BNZ-loaded cationic has great potential as a chemotherapeutic application of benznidazole. Copyright © 2017. Published by Elsevier B.V.

  9. Using Peephole Optimization on Intermediate Code

    NARCIS (Netherlands)

    Tanenbaum, A.S.; van Staveren, H.; Stevenson, J.W.

    1982-01-01

    Many portable compilers generate an intermediate code that is subsequently translated into the target machine's assembly language. In this paper a stack-machine-based intermediate code suitable for algebraic languages (e.g., PASCAL, C, FORTRAN) and most byte-addressed mini- and microcomputers is

  10. Gasoline Engine Mechanics. Performance Objectives. Intermediate Course.

    Science.gov (United States)

    Jones, Marion

    Several intermediate performance objectives and corresponding criterion measures are listed for each of six terminal objectives presented in this curriculum guide for an intermediate gasoline engine mechanics course at the secondary level. (For the beginning course guide see CE 010 947.) The materials were developed for a two-semester (2 hour…

  11. Some Intermediate-Level Violin Concertos.

    Science.gov (United States)

    Abramson, Michael

    1997-01-01

    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,…

  12. 39 CFR 3001.39 - Intermediate decisions.

    Science.gov (United States)

    2010-07-01

    ... 39 Postal Service 1 2010-07-01 2010-07-01 false Intermediate decisions. 3001.39 Section 3001.39 Postal Service POSTAL REGULATORY COMMISSION PERSONNEL RULES OF PRACTICE AND PROCEDURE Rules of General Applicability § 3001.39 Intermediate decisions. (a) Initial decision by presiding officer. In any proceedings in...

  13. Pair production of intermediate vector bosons

    International Nuclear Information System (INIS)

    Mikaelian, K.O.

    1979-01-01

    The production of intermediate vector boson pairs W + W - , Z 0 Z 0 , W +- Z 0 and W +- γ in pp and p anti p collisions is discussed. The motivation is to detect the self-interactions among the four intermediate vector bosons

  14. Retention of intermediate polarization states in ferroelectric materials enabling memories for multi-bit data storage

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Dong; Asadi, Kamal; Blom, Paul W. M.; Leeuw, Dago M. de, E-mail: deleeuw@mpip-mainz.mpg.de [Max-Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz (Germany); Katsouras, Ilias [Holst Centre, High Tech Campus 31, 5656AE Eindhoven (Netherlands); Groen, Wilhelm A. [Holst Centre, High Tech Campus 31, 5656AE Eindhoven (Netherlands); Faculty of Aerospace Engineering, Delft University of Technology, Kluyverweg 1 2629 HS, Delft (Netherlands)

    2016-06-06

    A homogeneous ferroelectric single crystal exhibits only two remanent polarization states that are stable over time, whereas intermediate, or unsaturated, polarization states are thermodynamically instable. Commonly used ferroelectric materials however, are inhomogeneous polycrystalline thin films or ceramics. To investigate the stability of intermediate polarization states, formed upon incomplete, or partial, switching, we have systematically studied their retention in capacitors comprising two classic ferroelectric materials, viz. random copolymer of vinylidene fluoride with trifluoroethylene, P(VDF-TrFE), and Pb(Zr,Ti)O{sub 3}. Each experiment started from a discharged and electrically depolarized ferroelectric capacitor. Voltage pulses were applied to set the given polarization states. The retention was measured as a function of time at various temperatures. The intermediate polarization states are stable over time, up to the Curie temperature. We argue that the remarkable stability originates from the coexistence of effectively independent domains, with different values of polarization and coercive field. A domain growth model is derived quantitatively describing deterministic switching between the intermediate polarization states. We show that by using well-defined voltage pulses, the polarization can be set to any arbitrary value, allowing arithmetic programming. The feasibility of arithmetic programming along with the inherent stability of intermediate polarization states makes ferroelectric materials ideal candidates for multibit data storage.

  15. Retention of intermediate polarization states in ferroelectric materials enabling memories for multi-bit data storage

    Science.gov (United States)

    Zhao, Dong; Katsouras, Ilias; Asadi, Kamal; Groen, Wilhelm A.; Blom, Paul W. M.; de Leeuw, Dago M.

    2016-06-01

    A homogeneous ferroelectric single crystal exhibits only two remanent polarization states that are stable over time, whereas intermediate, or unsaturated, polarization states are thermodynamically instable. Commonly used ferroelectric materials however, are inhomogeneous polycrystalline thin films or ceramics. To investigate the stability of intermediate polarization states, formed upon incomplete, or partial, switching, we have systematically studied their retention in capacitors comprising two classic ferroelectric materials, viz. random copolymer of vinylidene fluoride with trifluoroethylene, P(VDF-TrFE), and Pb(Zr,Ti)O3. Each experiment started from a discharged and electrically depolarized ferroelectric capacitor. Voltage pulses were applied to set the given polarization states. The retention was measured as a function of time at various temperatures. The intermediate polarization states are stable over time, up to the Curie temperature. We argue that the remarkable stability originates from the coexistence of effectively independent domains, with different values of polarization and coercive field. A domain growth model is derived quantitatively describing deterministic switching between the intermediate polarization states. We show that by using well-defined voltage pulses, the polarization can be set to any arbitrary value, allowing arithmetic programming. The feasibility of arithmetic programming along with the inherent stability of intermediate polarization states makes ferroelectric materials ideal candidates for multibit data storage.

  16. Intermediates and the folding of proteins L and G

    Energy Technology Data Exchange (ETDEWEB)

    Brown, Scott; Head-Gordon, Teresa

    2003-07-01

    We use a minimalist protein model, in combination with a sequence design strategy, to determine differences in primary structure for proteins L and G that are responsible for the two proteins folding through distinctly different folding mechanisms. We find that the folding of proteins L and G are consistent with a nucleation-condensation mechanism, each of which is described as helix-assisted {beta}-1 and {beta}-2 hairpin formation, respectively. We determine that the model for protein G exhibits an early intermediate that precedes the rate-limiting barrier of folding and which draws together misaligned secondary structure elements that are stabilized by hydrophobic core contacts involving the third {beta}-strand, and presages the later transition state in which the correct strand alignment of these same secondary structure elements is restored. Finally the validity of the targeted intermediate ensemble for protein G was analyzed by fitting the kinetic data to a two-step first order reversible reaction, proving that protein G folding involves an on-pathway early intermediate, and should be populated and therefore observable by experiment.

  17. Electron-atom scattering at intermediate energies

    International Nuclear Information System (INIS)

    Kingston, A.E.; Walters, H.R.J.

    1982-01-01

    The problems of intermediate energy scattering are approached from the low and high energy ends. At low intermediate energies difficulties associated with the use of pseudostates and correlation terms are discussed, special consideration being given to nonphysical pseudoresonances. Perturbation methods appropriate to high intermediate energies are described and attempts to extend these high energy approximations down to low intermediate energies are studied. It is shown how the importance of electron exchange effects develops with decreasing energy. The problem of assessing the 'effective completeness' of pseudostate sets at intermediate energies is mentioned and an instructive analysis of a 2p pseudostate approximation to elastic e - -H scattering is given. It is suggested that at low energies the Pauli Exclusion Principle can act to hide short range defects in pseudostate approximations. (author)

  18. Application of edible paraffin oil for cationic dye removal from water using emulsion liquid membrane.

    Science.gov (United States)

    Zereshki, Sina; Daraei, Parisa; Shokri, Amin

    2018-05-18

    Using an emulsion liquid membrane based on edible oils is investigated for removing cationic dyes from aqueous solutions. There is a great potential for using edible oils in food industry extraction processes. The parameters affecting the stability of the emulsion and the extraction rate were studied. These parameters were the emulsification time, the stirring speed, the surfactant concentration, the internal phase concentration, the feed phase concentration, the volume ratio of internal phase to organic phase and the treat ratio. In order to stabilize the emulsion without using a carrier, edible paraffin oil and heptane are used at an 80:20 ratio. The optimum conditions for the extraction of methylene blue (MB), crystal violet and methyl violet (CV and MV) cationic dyes using edible paraffin oil as an environment friendly solvent are represented. A removal percentage of 95% was achieved for a mixture of dyes. The optimum concentration of sodium hydroxide in the internal phase, which results a stabile emulsion with a high stripping efficiency of 96%, was 0.04 M. An excellent membrane recovery was observed and the extraction of dyes did not decrease up to seven run cycles. Copyright © 2018 Elsevier B.V. All rights reserved.

  19. Cation depletion by the sodium pump in red cells with pathologic cation leaks. Sickle cells and xerocytes.

    OpenAIRE

    Joiner, C H; Platt, O S; Lux, S E

    1986-01-01

    The mechanism by which sickle cells and xerocytic red cells become depleted of cations in vivo has not been identified previously. Both types of cells exhibit elevated permeabilities to sodium and potassium, in the case of sickle cells, when deoxygenated. The ouabain-insensitive fluxes of sodium and potassium were equivalent, however, in both cell types under these conditions. When incubated 18 hours in vitro, sickle cells lost cations but only when deoxygenated. This cation depletion was blo...

  20. Experimental and theoretical study of 2,6-difluorophenylnitrene, its radical cation, and their rearrangement products in argon matrices.

    Science.gov (United States)

    Carra, Claudio; Nussbaum, Rafael; Bally, Thomas

    2006-06-12

    2,6-Difluorophenylnitrene was reinvestigated both experimentally, in Ar matrices at 10 K, and computationally, by DFT and CASSCF/CASPT2 calculations. Almost-pure samples of both neutral rearrangement products (the bicyclic azirine and the cyclic ketenimine) of a phenylnitrene were prepared and characterized for the first time. These samples were then subjected to X-irradiation in the presence of CH2Cl2 as an electron scavenger, which led to ionization of the neutral intermediates. Thereby, it was shown that only the phenylnitrene and the cyclic ketenimine yield stable radical cations, whereas the bicyclic azirine decays to both of these compounds on ionization. The cyclic ketenimine yields a novel aromatic azatropylium-type radical cation. The electronic structure of the title compound is discussed in detail, and its relation to those of the iso-pi-electronic benzyl radical and phenylcarbene is traced.

  1. 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.

    Science.gov (United States)

    Bahrami, Homayoon; Farhadi, Saeed; Siadatnasab, Firouzeh

    2016-07-01

    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) 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.

  2. Predicting Organic Cation Sorption Coefficients: Accounting for Competition from Sorbed Inorganic Cations Using a Simple Probe Molecule.

    Science.gov (United States)

    Jolin, William C; Goyetche, Reaha; Carter, Katherine; Medina, John; Vasudevan, Dharni; MacKay, Allison A

    2017-06-06

    With the increasing number of emerging contaminants that are cationic at environmentally relevant pH values, there is a need for robust predictive models of organic cation sorption coefficients (K d ). Current predictive models fail to account for the differences in the identity, abundance, and affinity of surface-associated inorganic exchange ions naturally present at negatively charged receptor sites on environmental solids. To better understand how organic cation sorption is influenced by surface-associated inorganic exchange ions, sorption coefficients of 10 organic cations (including eight pharmaceuticals and two simple probe organic amines) were determined for six homoionic forms of the aluminosilicate mineral, montmorillonite. Organic cation sorption coefficients exhibited consistent trends for all compounds across the various homoionic clays with sorption coefficients (K d ) decreasing as follows: K d Na + > K d NH 4 + ≥ K d K + > K d Ca 2+ ≥ K d Mg 2+ > K d Al 3+ . This trend for competition between organic cations and exchangeable inorganic cations is consistent with the inorganic cation selectivity sequence, determined for exchange between inorganic ions. Such consistent trends in competition between organic and inorganic cations suggested that a simple probe cation, such as phenyltrimethylammonium or benzylamine, could capture soil-to-soil variations in native inorganic cation identity and abundance for the prediction of organic cation sorption to soils and soil minerals. Indeed, sorption of two pharmaceutical compounds to 30 soils was better described by phenyltrimethylammonium sorption than by measures of benzylamine sorption, effective cation exchange capacity alone, or a model from the literature (Droge, S., and Goss, K. Environ. Sci. Technol. 2013, 47, 14224). A hybrid approach integrating structural scaling factors derived from this literature model of organic cation sorption, along with phenyltrimethylammonium K d values, allowed for

  3. Computational study of cation substitutions in apatites

    International Nuclear Information System (INIS)

    Tamm, Toomas; Peld, Merike

    2006-01-01

    Density-functional theory plane-wave modeling of fluor- and hydroxyapatites has been performed, where one or two calcium ions per unit cell were replaced with cadmium or zinc cations. It was found that cadmium ions favor Ca(1) positions in fluorapatites and Ca(2) positions in hydroxyapatites, in agreement with experiment. A similar pattern is predicted for zinc substitutions. In the doubly substituted cases, where only hydroxyapatites were modeled, a preference for the substituting ions to be located in Ca(2) position was also observed. Displacement of the hydroxide ions from their symmetrical positions on the hexagonal axis can be used to explain the preferred configurations of substituting ions around the axis. -- Deformation of the hydroxide ion chain due to substitutions around the ion channel in substituted hydroxyapatites

  4. Retention of Cationic Starch onto Cellulose Fibres

    Science.gov (United States)

    Missaoui, Mohamed; Mauret, Evelyne; Belgacem, Mohamed Naceur

    2008-08-01

    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.

  5. Repurposing Cationic Amphiphilic Antihistamines for Cancer Treatment

    DEFF Research Database (Denmark)

    Ellegaard, Anne-Marie; Dehlendorff, Christian; Vind, Anna C.

    2016-01-01

    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...

  6. Use of a material conducting hydrogen cations

    International Nuclear Information System (INIS)

    Howe, A.T.; Shilton, M.G.

    1986-01-01

    The invention concerns a separator conducting hydrogenous for electrical devices, which contains at least one compound with the formula H(UO 2 )PO 4 x nH 2 O, H(UO 2 )AsO 4 x nH 2 O or H(UO 2 )IO 4 (OH) 2 x nH 2 O, where not more than 50% by weight of the H + is replaced by one or more cations, such as Li + , Na + , K + , NH 4 + , Cu 2+ , Mg 2+ , Ca 2+ , Ba 2+ , Sr 2+ , Pb 2+ , Fe 2+ , Co 2+ , Ni 2+ , Mn 2+ or Al 3+ . The electrical device having the separator can be an electrolysis cell, for example, an electro chromium cell. (H x WO 3 ), a hydrogen isotope enrichment device, a proton-sensitive electrode (eg for a pH meter), a battery or a fuel cell. (orig./MM) [de

  7. A Cationic Smart Copolymer for DNA Binding

    Directory of Open Access Journals (Sweden)

    Tânia Ribeiro

    2017-11-01

    Full Text Available A new block copolymer with a temperature-responsive block and a cationic block was prepared by reversible addition-fragmentation chain transfer (RAFT polymerization, with good control of its size and composition. The first block is composed by di(ethylene glycol methyl ether methacrylate (DEGMA and oligo(ethylene glycol methyl ether methacrylate (OEGMA, with the ratio DEGMA/OEGMA being used to choose the volume phase transition temperature of the polymer in water, tunable from ca. 25 to above 90 °C. The second block, of trimethyl-2-methacroyloxyethylammonium chloride (TMEC, is positively charged at physiological pH values and is used for DNA binding. The coacervate complexes between the block copolymer and a model single strand DNA are characterized by fluorescence correlation spectroscopy and fluorescence spectroscopy. The new materials offer good prospects for biomedical application, for example in controlled gene delivery.

  8. Hydration Structure of the Quaternary Ammonium Cations

    KAUST Repository

    Babiaczyk, Wojtek Iwo

    2010-11-25

    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.

  9. Calixarenes synthesized for seducing and trapping cations

    International Nuclear Information System (INIS)

    Dozol, J.F.

    1997-01-01

    Calixarenes are known to be selective extractants for cesium radioactive cations. This liquid-liquid extraction is still to be studied and would allow to reduce the volume of years living radioactive wastes before they were stored and perhaps to remove then the cesium by transmutation. Calixarenes are macrocycles with phenolic units bridged by methylene groups. They have the important property to have a flexible structure. On this basic structure, all kinds of chemical functions can be branched. They thus confer particular properties to the molecule. A computerized virtual construction phase of molecules is actually studied in order to optimize the extraction. It is currently known that with small modifications it will be possible to selectively extract heavy metals (Hg, Cd..) coming from industrial pollution. (O.M.)

  10. 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)

    2007-06-11

    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

  11. Magnetic Resonance Studies of Proton Loss from Carotenoid Radical Cations

    International Nuclear Information System (INIS)

    Kispert, Lowell D.; Focsan, A. Ligia; Konovalova, Tatyana A.; Lawrence, Jesse; Bowman, Michael K.; Dixon, David A.; Molnar, Peter; Deli, Jozsef

    2007-01-01

    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 ((number s ign)Car · ) by proton loss from the methyl groups at positions 5 or 5(prime), and possibly 9 or 9(prime) and 13 or 13(prime). 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 # center d ot# + which agree with the ENDOR for carotenoid π-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(prime)-apo-β-caroten-8(prime)-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(prime)), 9(9(prime)) or 13(13(prime)) methyl positions has importance in photoprotection. Photoprotection involves nonphotochemical quenching (NPQ) in which 1 Ch1* 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 # center d ot# + ...Chl # center d ot# - ), lower in

  12. Safety evaluation of cation-exchange resins

    International Nuclear Information System (INIS)

    Kalkwarf, D.R.

    1977-08-01

    Results are presented of a study to evaluate whether sufficient information is available to establish conservative limits for the safe use of cation-exchange resins in separating radionuclides and, if not, to recommend what new data should be acquired. The study was also an attempt to identify in-line analytical techniques for the evaluation of resin degradation during radionuclide processing. The report is based upon a review of the published literature and upon discussions with many people engaged in the use of these resins. It was concluded that the chief hazard in the use of cation-exchange resins for separating radionuclides is a thermal explosion if nitric acid or other strong oxidants are present in the process solution. Thermal explosions can be avoided by limiting process parameters so that the rates of heat and gas generation in the system do not exceed the rates for their transfer to the surroundings. Such parameters include temperature, oxidant concentration, the amounts of possible catalysts, the radiation dose absorbed by the resin and the diameter of the resin column. Current information is not sufficient to define safe upper limits for these parameters. They can be evaluated, however, from equations derived from the Frank-Kamenetskii theory of thermal explosions provided the heat capacities, thermal conductivities and rates of heat evolution in the relevant resin-oxidant mixtures are known. It is recommended that such measurements be made and the appropriate limits be evaluated. A list of additional safety precautions are also presented to aid in the application of these limits and to provide additional margins of safety. In-line evaluation of resin degradation to assess its safety hazard is considered impractical. Rather, it is recommended that the resin be removed from use before it has received the limiting radiation dose, evaluated as described above

  13. A review of modelling the interaction between natural organic matter and metal cations

    International Nuclear Information System (INIS)

    Falck, W.E.

    1989-01-01

    This report reviews techniques available to model the interaction between natural organic matter (mainly fulvic and humic acids) and metal cations and protons. A comprehensive overview over the properties of natural organic matter is given and experimental techniques are presented briefly. Two major concepts of modelling have been identified: discrete ligand models and continuous distribution model. Different modelling approaches like Discrete Ligand Models (s.s.), Random-Structure Model, Affinity Spectra, Statistical Distribution Models, Continuous Stability Function Models and surface sorption models and their advantages/disadvantages are discussed. (author)

  14. Impact of cationic diffusion on properties of iron-bearing glass fibres

    DEFF Research Database (Denmark)

    Smedskjaer, Morten M.; Yue, Yuanzheng; Deubener, Joachim

    2010-01-01

    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...

  15. Adiabatic differential scanning calorimetric study of divalent cation induced DNA - DPPC liposome formulation compacted for gene delivery

    Directory of Open Access Journals (Sweden)

    Erhan Süleymanoglu

    2004-11-01

    Full Text Available Complexes between nucleic acids and phospholipid vesicles have been developed as stable non-viral gene delivery vehicles. Currently employed approach uses positively charged lipid species and a helper zwitterionic lipid, the latter being applied for the stabilization of the whole complex. However, besides problematic steps during their preparation, cationic lipids are toxic for cells. The present work describes some energetic issues pertinent to preparation and use of neutral lipid-DNA self-assemblies, thus avoiding toxicity of lipoplexes. Differential scanning calorimetry data showed stabilization of polynucleotide helix upon its interaction with liposomes in the presence of divalent metal cations. It is thus possible to suggest this self-assembly as an improved formulation for use in gene delivery.

  16. 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

    2016-06-01

    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.

  17. The effect of various electrolyte cations on electrochemical performance of polypyrrole/RGO based supercapacitors.

    Science.gov (United States)

    Zhu, Jianbo; Xu, Youlong; Wang, Jie; Lin, Jun; Sun, Xiaofei; Mao, Shengchun

    2015-11-21

    In this work, polypyrrole/graphene doped by p-toluenesulfonic is prepared as an active material for supercapacitors, and its capacitance performance is investigated in various aqueous electrolytes including HCl, LiCl, NaCl, and KCl with a concentration of 3 M, respectively. A rising trend of capacitance is observed according to the cationic mobility (Li(+) Na(+) > Li(+) > H(+)). The reason can be attributed to the fact that the insertion/de-insertion of large size cation brings a significant doping level decrease and an over-oxidation increase during the charging-discharging cycles. Hence, we not only obtain good capacitance performance (280.3 F g(-1) at 5 mV s(-1)), superior rate capability (225.8 F g(-1) at 500 mV s(-1)) and high cycling stability (92.0% capacitance retention after 10,000 cycles at 1 A g(-1)) by employing 3 M HCl as an electrolyte, but also reveal that the electrolyte cations have a significant effect on the supercapacitors' electrochemical performance.

  18. Radiation induced graft copolymerization for preparation of cation exchange membranes: a review

    International Nuclear Information System (INIS)

    Mohamed Mahmoud Nasef; Hamdani Saidi; Hussin Mohd Nor

    1999-01-01

    Cation exchange membranes are regarded as the ideal solid polymer electrolyte materials for the development of various electrochemical energy conversion applications where significant improvements in the current density are required. Such membranes require special polymers and preparation techniques to maintain high chemical , mechanical and thermal stability in addition to high ionic conductivity and low resistance. A lot of different techniques have been proposed in the past to prepare such membranes. Radiation-induced graft copolymerization provides an attractive ft method for modification of chemical and physical properties of polymeric materials and is of particular interest in achieving specially desired cation exchange membranes as well as excellent membrane properties. This is due to the ability to control the membrane compositions as well as properties by proper selection of grafting conditions. Therefore numerous parameters have to be investigated to properly select the right polymeric materials, radiation grafting technique and the grafting conditions to be employed. In this paper a state-of-the-art of radiation-induced graft copolymerization for preparation of cation exchange membranes and their applications are briefly reviewed. (Author)

  19. Kinetic Monte Carlo Simulation of Cation Diffusion in Low-K Ceramics

    Science.gov (United States)

    Good, Brian

    2013-01-01

    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.

  20. Dimerization of human immunodeficiency virus (type 1) RNA: stimulation by cations and possible mechanism.

    Science.gov (United States)

    Marquet, R; Baudin, F; Gabus, C; Darlix, J L; Mougel, M; Ehresmann, C; Ehresmann, B

    1991-05-11

    The retroviral genome consists of two identical RNA molecules joined close to their 5' ends by the dimer linkage structure. Recent findings indicated that retroviral RNA dimerization and encapsidation are probably related events during virion assembly. We studied the cation-induced dimerization of HIV-1 RNA and results indicate that all in vitro generated HIV-1 RNAs containing a 100 nucleotide domain downstream from the 5' splice site are able to dimerize. RNA dimerization depends on the concentration of RNA, mono- and multivalent cations, the size of the monovalent cation, temperature, and pH. Up to 75% of HIV-1 RNA is dimeric in the presence of spermidine. HIV-1 RNA dimer is fairly resistant to denaturing agents and unaffected by intercalating drugs. Antisense HIV-1 RNA does not dimerize but heterodimers can be formed between HIV-1 RNA and either MoMuLV or RSV RNA. Therefore retroviral RNA dimerization probably does not simply proceed through mechanisms involving Watson-Crick base-pairing. Neither adenine and cytosine protonation, nor quartets containing only guanines appear to determine the stability of the HIV-1 RNA dimer, while quartets involving both adenine(s) and guanine(s) could account for our results. A consensus sequence PuGGAPuA found in the putative dimerization-encapsidation region of all retroviral genomes examined may participate in the dimerization process.

  1. Efficient Removal of Cationic and Anionic Radioactive Pollutants from Water Using Hydrotalcite-Based Getters.

    Science.gov (United States)

    Bo, Arixin; Sarina, Sarina; Liu, Hongwei; Zheng, Zhanfeng; Xiao, Qi; Gu, Yuantong; Ayoko, Godwin A; Zhu, Huaiyong

    2016-06-29

    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.

  2. Strontium isotopes provide clues for a process shift in base cation dynamics in young volcanic soils

    Science.gov (United States)

    Bingham, N.; Jackson, M. G.; Bookhagen, B.; Maher, K.; Chadwick, O.

    2015-12-01

    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

  3. Effects of metallic cations in the beryl flotation

    International Nuclear Information System (INIS)

    Lima Leonel, C.M. de; Peres, A.E.C.

    1984-01-01

    The beryl zeta potential in microelectrophoretic cell is studied in the presence of neutral electrolyte, cations of calcium, magnesium and iron. The petroleum sulfonate is used how collector in Hallimond tube. Hydroxy complex of metallic cations seems activate the ore and precipitates of colloidal metallic hidroxies seems lower him when added to the mixture. (M.A.C.) [pt

  4. Stable polyfluorinated cycloalkenyl cations and their NMR spectra

    International Nuclear Information System (INIS)

    Snegirev, V.F.; Galakhov, M.V.; Makarov, K.N.; Bakhmutov, V.I.

    1986-01-01

    New stable 1-methoxyperfluoro-2-ethylcyclobutenyl, 1-methoxyperfluoro-2-methylcyclo-pentenyl, and 1-methoxyperfluoro-2-ethylcyclohexenyl cations were obtained by the action of antimony pentafluoride on the corresponding olefins. The distribution of the charges in the investigated polyfluorinated cycloalkenyl cations was investigated by 13 C NMR method

  5. Synthesis of Cationic Core-Shell Latex Particles

    NARCIS (Netherlands)

    Dziomkina, N.; Hempenius, Mark A.; Vancso, Gyula J.

    2006-01-01

    Surfactant-free seeded (core-shell) polymerization of cationic polymer colloids is presented. Polystyrene core particles with sizes between 200 nm and 500 nm were synthesized. The number average diameter of the colloidal core particles increased with increasing monomer concentration. Cationic shells

  6. Cationic antimicrobial peptides inactivate Shiga toxin-encoding bacteriophages

    Science.gov (United States)

    Del Cogliano, Manuel E.; Hollmann, Axel; Martinez, Melina; Semorile, Liliana; Ghiringhelli, Pablo D.; Maffía, Paulo C.; Bentancor, Leticia V.

    2017-12-01

    Shiga toxin (Stx) is the principal virulence factor during Shiga toxin-producing Escherichia coli (STEC) infections. We have previously reported the inactivation of bacteriophage encoding Stx after treatment with chitosan, a linear polysaccharide polymer with cationic properties. Cationic antimicrobial peptides (cAMPs) are short linear aminoacidic sequences, with a positive net charge, which display bactericidal or bacteriostatic activity against a wide range of bacterial species. They are promising novel antibiotics since they have shown bactericidal effects against multiresistant bacteria. To evaluate whether cationic properties are responsible for bacteriophage inactivation, we tested seven cationic peptides with proven antimicrobial activity as anti-bacteriophage agents, and one random sequence cationic peptide with no antimicrobial activity as a control. We observed bacteriophage inactivation after incubation with five cAMPs, but no inactivating activity was observed with the random sequence cationic peptide or with the non alpha helical cAMP Omiganan. Finally, to confirm peptide-bacteriophage interaction, zeta potential was analyzed by following changes on bacteriophage surface charges after peptide incubation. According to our results we could propose that: 1) direct interaction of peptides with phage is a necessary step for bacteriophage inactivation, 2) cationic properties are necessary but not sufficient for bacteriophage inactivation, and 3) inactivation by cationic peptides could be sequence (or structure) specific. Overall our data suggest that these peptides could be considered a new family of molecules potentially useful to decrease bacteriophage replication and Stx expression.

  7. CATION EXCHANGE METHOD FOR THE RECOVERY OF PROTACTINIUM

    Science.gov (United States)

    Studier, M.H.; Sullivan, J.C.

    1959-07-14

    A cation exchange prccess is described for separating protactinium values from thorium values whereby they are initially adsorbed together from an aqueous 0.1 to 2 N hydrochloric acid on a cation exchange resin in a column. Then selectively eluting the thorium by an ammonium sulfate solution and subsequently eluting the protactinium by an oxalate solution.

  8. pi-Dimers of end-capped oligopyrrole cation radicals

    NARCIS (Netherlands)

    Haare, van J.A.E.H.; Groenendaal, L.; Havinga, E.E.; Janssen, R.A.J.; Meijer, E.W.

    1996-01-01

    In two consecutive one-electron oxidations, oligopyrroles substituted with phenyl capping groups (PhPynPh, n = 2–4) can be oxidized reversibly to give stable cation radicals and dications. Spectroelectrochemical studies give direct evidence that diamagnetic p-dimers of cation radicals are formed in

  9. Cation exchange of 53 elements in nitric acid

    International Nuclear Information System (INIS)

    Marsh, S.F.; Alarid, J.E.; Hamond, C.F.; McLeod, M.J.; Roensch, F.R.; Rein, J.E.

    1978-02-01

    Cation-exchange distribution data are presented for 53 elements from 3 to 12M HNO 3 for three strong-acid resins, having cross-linkages of 8%, 4%, and macroporous. Data obtained by 16- to 18-h dynamic batch contacts are compared to cation-exchange distribution data from strong HCl and HClO 4

  10. Base Cation Leaching From the Canopy of a Rubber ( Hevea ...

    African Journals Online (AJOL)

    Base cations are essential to the sustainability of forest ecosystems. They are important for neutralizing the acidifying effects of atmospheric deposition. There is the need for in-depth understanding of base cation depletion and leaching from forest canopy. This is important particularly due to the increasing acidification and ...

  11. Cationic Antimicrobial Peptides Inactivate Shiga Toxin-Encoding Bacteriophages

    Directory of Open Access Journals (Sweden)

    Manuel E. Del Cogliano

    2017-12-01

    Full Text Available Shiga toxin (Stx is the principal virulence factor during Shiga toxin-producing Escherichia coli (STEC infections. We have previously reported the inactivation of bacteriophage encoding Stx after treatment with chitosan, a linear polysaccharide polymer with cationic properties. Cationic antimicrobial peptides (cAMPs are short linear aminoacidic sequences, with a positive net charge, which display bactericidal or bacteriostatic activity against a wide range of bacterial species. They are promising novel antibiotics since they have shown bactericidal effects against multiresistant bacteria. To evaluate whether cationic properties are responsible for bacteriophage inactivation, we tested seven cationic peptides with proven antimicrobial activity as anti-bacteriophage agents, and one random sequence cationic peptide with no antimicrobial activity as a control. We observed bacteriophage inactivation after incubation with five cAMPs, but no inactivating activity was observed with the random sequence cationic peptide or with the non-alpha helical cAMP Omiganan. Finally, to confirm peptide-bacteriophage interaction, zeta potential was analyzed by following changes on bacteriophage surface charges after peptide incubation. According to our results we could propose that: (1 direct interaction of peptides with phage is a necessary step for bacteriophage inactivation, (2 cationic properties are necessary but not sufficient for bacteriophage inactivation, and (3 inactivation by cationic peptides could be sequence (or structure specific. Overall our data suggest that these peptides could be considered a new family of molecules potentially useful to decrease bacteriophage replication and Stx expression.

  12. Cation substitution induced blue-shift of optical band gap

    Indian Academy of Sciences (India)

    Cation substitution induced blue-shift of optical band gap in nanocrystalline Zn ( 1 − x ) Ca x O thin films deposited by sol–gel dip coating technique ... thin films giving 13.03% enhancement in theenergy gap value due to the electronic perturbation caused by cation substitution as well as deterioration in crystallinity.

  13. In vivo toxicity of cationic micelles and liposomes

    DEFF Research Database (Denmark)

    Knudsen, Kristina Bram; Northeved, Helle; Ek, Pramod Kumar

    2015-01-01

    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 las...

  14. Uranium adsorption from the sulphuric acid leach liquor containing more chlorides with cation-exchange resin SL-406

    International Nuclear Information System (INIS)

    Hu Jun; Wang Zhaoguo; Chi Renqing; Niu Xuejun

    1994-01-01

    The feasibility of uranium adsorption was studied from the sulphuric acid leach liquor of a uranium ore containing more chlorides with cation-exchange resin SL-406. The influence of some factors on uranium adsorption was investigated. It was shown that the resin possesses better selectivity, stability and higher capacity. It can be effectively used to recovery uranium from leach liquors of uranium ores containing more chlorides

  15. Inversion of membrane surface charge by trivalent cations probed with a cation-selective channel.

    Science.gov (United States)

    Gurnev, Philip A; Bezrukov, Sergey M

    2012-11-13

    We demonstrate that the cation-selective channel formed by gramicidin A can be used as a reliable sensor for studying the multivalent ion accumulation at the surfaces of charged lipid membranes and the "charge inversion" phenomenon. In asymmetrically charged membranes with the individual leaflets formed from pure negative and positive lipids bathed by 0.1 M CsCl solutions the channel exhibits current rectification, which is comparable to that of a typical n/p semiconductor diode. We show that even at these highly asymmetrical conditions the channel conductance can be satisfactorily described by the electrodiffusion equation in the constant field approximation but, due to predictable limitations, only when the applied voltages do not exceed 50 mV. Analysis of the changes in the voltage-dependent channel conductance upon addition of trivalent cations allows us to gauge their interactions with the membrane surface. The inversion of the sign of the effective surface charge takes place at the concentrations, which correlate with the cation size. Specifically, these concentrations are close to 0.05 mM for lanthanum, 0.25 mM for hexaamminecobalt, and 4 mM for spermidine.

  16. Language in use intermediate : classroom book

    CERN Document Server

    Doff, Adrian

    1995-01-01

    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 www.cambridge.org/elt/liu or contact your local Cambridge University Press representative.

  17. Language in use intermediate : teacher's book

    CERN Document Server

    Doff, Adrian

    1998-01-01

    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 www.cambridge.org/elt/liu or contact your local Cambridge University Press representative.

  18. Glutamate Induced Thermal Equilibrium Intermediate and Counteracting Effect on Chemical Denaturation of Proteins.

    Science.gov (United States)

    Anumalla, Bramhini; Prabhu, N Prakash

    2018-01-25

    When organisms are subjected to stress conditions, one of their adaptive responses is accumulation of small organic molecules called osmolytes. These osmolytes affect the structure and stability of the biological macromolecules including proteins. The present study examines the effect of a negatively charged amino acid osmolyte, glutamate (Glu), on two model proteins, ribonuclease A (RNase A) and α-lactalbumin (α-LA), which have positive and negative surface charges at pH 7, respectively. These proteins follow two-state unfolding transitions during both heat and chemical induced denaturation processes. The addition of Glu stabilizes the proteins against temperature and induces an early equilibrium intermediate during unfolding. The stability is found to be enthalpy-driven, and the free energy of stabilization is more for α-LA compared to RNase A. The decrease in the partial molar volume and compressibility of both of the proteins in the presence of Glu suggests that the proteins attain a more compact state through surface hydration which could provide a more stable conformation. This is also supported by molecule dynamic simulation studies which demonstrate that the water density around the proteins is increased upon the addition of Glu. Further, the intermediates could be completely destabilized by lower concentrations (∼0.5 M) of guanidinium chloride and salt. However, urea subverts the Glu-induced intermediate formed by α-LA, whereas it only slightly destabilizes in the case of RNase A which has a positive surface charge and could possess charge-charge interactions with Glu. This suggests that, apart from hydration, columbic interactions might also contribute to the stability of the intermediate. Gdm-induced denaturation of RNase A and α-LA in the absence and the presence of Glu at different temperatures was carried out. These results also show the Glu-induced stabilization of both of the proteins; however, all of the unfolding transitions followed two

  19. Cation interdiffusion in polycrystalline calcium and strontium titanate

    International Nuclear Information System (INIS)

    Butler, E.P.; Jain, H.; Smyth, D.M.

    1991-01-01

    This paper discusses a method that has been developed to study bulk lattice interdiffusion between calcium and strontium titanate by fabrication of a diffusion couple using cosintering. The measured interdiffusion coefficients, D(C), indicate that strontium impurity diffusion in calcium titanate occurs at a faster rate than calcium impurity diffusion in strontium titanate. These interdiffusion coefficients are composition independent when the concentration of the calcium cation exceeds that of the strontium cation; otherwise D(C) is strongly composition dependent. Investigations into the effect of cation nonstoichiometry give results that are consistent with a defect incorporation reaction in which excess TiO 2 , within the solid solubility limit, produces A-site cation vacancies as compensating defects. The interdiffusion coefficients increase with increasing concentrations of TiO 2 , so it is concluded that interdiffusion of these alkaline-earth cations in their titanates occurs via a vacancy mechanism

  20. Increasing Base Cations in Streams: Another Legacy of Deicing Salts?

    Science.gov (United States)

    Helton, A. M.; Barclay, J. R.; Bellucci, C.; Rittenhouse, C.

    2017-12-01

    Elevated use of deicing salts directly increases sodium chloride inputs to watersheds. Sodium can accumulate in soils over time and has the potential to leach other cations (e.g., calcium, magnesium, and potassium) from the soil through cation exchange. We hypothesize that increased use of deicing salts results in a legacy of soils depleted in non-sodium base cations with loss of cations to receiving waters. The goal of this project is to quantify temporal trends in base cations and chloride in streams and rivers across the United States. We used Weighted Regressions on Time, Discharge, and Season (WRTDS) to analyze trends in base cations. Our preliminary analysis of 10 rivers in Connecticut with chemical periods of record ranging from 24 - 64 years (median = 55 years), shows that the flux of base cations is increasing in all sites (25 - 366 103 meq ha-1 yr-1 yr-1), driven largely by increases in sodium (23 - 222 103 meq ha-1 yr-1 yr-1), the dominant cation in 7 of the sites. Chloride is also increasing at all sites (26 - 261 103 meq ha-1 yr-1 yr-1), which, in combination with salt use trends, suggests a road salt source for the increased sodium. Non-sodium cations are also increasing in 9 of the sites (8 - 54 103 meq ha-1 yr-1 yr-1), though they are not directly added with most deicing salts. We will compare these trends to other long-term sites across the United States, and quantify relationships between cation trends and land cover, road density, and snowfall.

  1. 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...

  2. Suppression of the two-dimensional electron gas in LaGaO3/SrTiO3 by cation intermixing

    KAUST Repository

    Nazir, S.; Amin, B.; Schwingenschlö gl, Udo

    2013-01-01

    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

  3. Anionic or Cationic S-Doping in Bulk Anatase TiO 2 : Insights on Optical Absorption from First Principles Calculations

    KAUST Repository

    Harb, Moussab; Sautet, P.; Raybaud, P.

    2013-01-01

    as a function of the chemical potential of oxygen and considering three relevant sulfur chemical doping agents (S 2, H2S, and thiourea). It highlights that cationic configurations (S4+ and S6+) are strongly stabilized in a wide range of oxygen chemical

  4. Reversible chain transfer between organoyttrium cations and aluminum : Synthesis of aluminum-terminated polyethylene with extremely narrow molecular-weight distribution

    NARCIS (Netherlands)

    Kretschmer, W.P.; Meetsma, A.; Hessen, B.; Schmalz, T.; Qayyum, S.; Kempe, R.

    2006-01-01

    Aminopyridinato-ligand-stabilized organoyttrium cations are accessible in very good yield through alkane elimination from trialkyl yttrium complexes with sterically demanding aminopyridines, followed by abstraction of one of the two alkyl functions using ammonium borates. At 80 degrees C and in the

  5. The deterioration of intermediate moisture foods

    Science.gov (United States)

    Labruza, T. P.

    1971-01-01

    Deteriorative reactions are low and food quality high if intermediate moisture content of a food is held at a water activity of 0.6 to 0.75. Information is of interest to food processing and packaging industry.

  6. Intermediate/Advanced Research Design and Statistics

    Science.gov (United States)

    Ploutz-Snyder, Robert

    2009-01-01

    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

  7. On intermediate structures in heavy ion reactions

    International Nuclear Information System (INIS)

    Rotter, I.

    1977-01-01

    The conceptions of the nuclear reaction theory are reinvestigated on the basis of the continuum shell model. The correlation of the resonance states via the continuum can lead to intermediate structures in the cross section. (Auth.)

  8. VUV photo-processing of PAH cations: quantitative study on the ionization versus fragmentation processes

    Science.gov (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.

    2016-01-01

    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. PMID:27212712

  9. VUV photo-processing of PAH cations: quantitative study on the ionization versus fragmentation processes.

    Science.gov (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

    2016-05-10

    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.

  10. VUV PHOTO-PROCESSING OF PAH CATIONS: QUANTITATIVE STUDY ON THE IONIZATION VERSUS FRAGMENTATION PROCESSES

    International Nuclear Information System (INIS)

    Zhen, Junfeng; Castillo, Sarah Rodriguez; Joblin, Christine; Mulas, Giacomo; Sabbah, Hassan; Giuliani, Alexandre; Nahon, Laurent; Martin, Serge; Champeaux, Jean-Philippe; Mayer, Paul M.

    2016-01-01

    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.

  11. VUV PHOTO-PROCESSING OF PAH CATIONS: QUANTITATIVE STUDY ON THE IONIZATION VERSUS FRAGMENTATION PROCESSES

    Energy Technology Data Exchange (ETDEWEB)

    Zhen, Junfeng; Castillo, Sarah Rodriguez; Joblin, Christine; Mulas, Giacomo; Sabbah, Hassan [Université de Toulouse, UPS-OMP, Institut de Recherche en Astrophysique et Planétologie, Toulouse (France); Giuliani, Alexandre; Nahon, Laurent [Synchrotron SOLEIL, LOrme des Merisiers, F-91192 Gif sur Yvette Cedex (France); Martin, Serge [Institut Lumière Matière, Université Lyon 1-CNRS, Université de Lyon, F-69622 Villeurbanne cedex (France); Champeaux, Jean-Philippe [Laboratoire Collisions Agrégats Réactivité, Université de Toulouse, UPS-IRSAMC, CNRS, 118 Route de Narbonne, Bat 3R1B4, F-31062 Toulouse Cedex 9 (France); Mayer, Paul M., E-mail: christine.joblin@irap.omp.eu [Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa K1N 6N5 (Canada)

    2016-05-10

    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.

  12. Cation depletion by the sodium pump in red cells with pathologic cation leaks. Sickle cells and xerocytes.

    Science.gov (United States)

    Joiner, C H; Platt, O S; Lux, S E

    1986-12-01

    The mechanism by which sickle cells and xerocytic red cells become depleted of cations in vivo has not been identified previously. Both types of cells exhibit elevated permeabilities to sodium and potassium, in the case of sickle cells, when deoxygenated. The ouabain-insensitive fluxes of sodium and potassium were equivalent, however, in both cell types under these conditions. When incubated 18 hours in vitro, sickle cells lost cations but only when deoxygenated. This cation depletion was blocked by ouabain, removal of external potassium, or pretreatment with 4,4'-diisothiocyanostilbene-2,2'-disulfonate, which blocks the increase in cation permeability induced by deoxygenation. The loss of cation exhibited by oxygenated xerocytes similarly incubated was also blocked by ouabain. These data support the hypothesis that the elevated "passive" cation fluxes of xerocytes and deoxygenated sickle cells are not directly responsible for cation depletion of these cells; rather, these pathologic leaks interact with the sodium pump to produce a net loss of cellular cation.

  13. Comparison of "type I" and "type II" organic cation transport by organic cation transporters and organic anion-transporting polypeptides

    NARCIS (Netherlands)

    Van Montfoort, JE; Muller, M; Groothuis, GMM; Meijer, DKF; Koepsell, H; Meier, PJ

    Previous inhibition studies with taurocholate and cardiac glycosides suggested the presence of separate uptake systems for small "type I" (system1) and for bulky "type II" (system2) organic cations in rat hepatocytes. To identify the transport systems involved in type I and type II organic cation

  14. 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.

    2013-01-01

    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

  15. Chromatographic cation exchange separation of decigram quantities of californium and other transplutonium elements

    Energy Technology Data Exchange (ETDEWEB)

    Benker, D.E.; Chattin, F.R.; Collins, E.D.; Knauer, J.B.; Orr, P.B.; Ross, R.G.; Wiggins, J.T.

    1980-01-01

    Decigram quantities of highly radioactive transplutonium elements are routinely partitioned at TRU by chromatographic elution from cation resin using AHIB eluent. By using two high-pressure ion exchange columns, a small one for the initial loading of the feed and a large one for the elution, batch runs containing up to 200 mg of /sup 252/Cf can be made in about 5 hours (2 hours to load the feed and 3 hours for the elution). The number of effluent product fractions and the amount of actinides that must be collected in intermediate fractions are minimized by monitoring response from a flow-through alpha-detector. This process has been reliable and relatively easy to operate, and will continue to be used for partitioning transplutonium elements at TRU.

  16. Has Banks’ Financial Intermediation Improved in Russia?

    OpenAIRE

    Fungachova, Z.; Solanko, L.

    2010-01-01

    The aim of this paper is to analyze the increasing importance of banks in the Russian economy over the period following the financial crisis of 1998. We use several measures to assess the role of banks in domestic financial intermediation in Russia. The traditional macro-level view is complemented by the analysis of sectoral financial flows as well as by insights from micro-level studies. All of these confirm that banks are becoming increasingly important in financial intermediation. We find ...

  17. Intermediate Inflation or Late Time Acceleration?

    International Nuclear Information System (INIS)

    Sanyal, A.K.

    2008-01-01

    The expansion rate of intermediate inflation lies between the exponential and power law expansion but corresponding accelerated expansion does not start at the onset of cosmological evolution. Present study of intermediate inflation reveals that it admits scaling solution and has got a natural exit form it at a later epoch of cosmic evolution, leading to late time acceleration. The corresponding scalar field responsible for such feature is also found to behave as a tracker field for gravity with canonical kinetic term.

  18. Cation-π interaction of the univalent sodium cation with [2.2.2]paracyclophane: Experimental and theoretical study

    Science.gov (United States)

    Makrlík, Emanuel; Sýkora, David; Böhm, Stanislav; Vaňura, Petr

    2018-02-01

    By employing electrospray ionization mass spectrometry (ESI-MS), it was proven experimentally that the univalent sodium cation (Na+) forms with [2.2.2]paracyclophane (C24H24) the cationic complex [Na(C24H24)]+. Further, applying quantum chemical DFT calculations, the most probable structure of the [Na(C24H24)]+ complex was derived. In the resulting complex with a symmetry very close to C3, the "central" cation Na+, fully located in the cavity of the parent [2.2.2]paracyclophane ligand, is bound to all three benzene rings of [2.2.2]paracyclophane via cation-π interaction. Finally, the interaction energy, E(int), of the considered cation-π complex [Na(C24H24)]+ was found to be -267.3 kJ/mol, confirming the formation of this fascinating complex species as well.

  19. Associations of Systemic Diseases with Intermediate Uveitis.

    Science.gov (United States)

    Shoughy, Samir S; Kozak, Igor; Tabbara, Khalid F

    2016-01-01

    To determine the associations of systemic diseases with intermediate uveitis. The medical records of 50 consecutive cases with intermediate uveitis referred to The Eye Center in Riyadh, Saudi Arabia, were reviewed. Age- and sex-matched patients without uveitis served as controls. Patients had complete ophthalmic and medical examinations. There were 27 male and 23 female patients. Mean age was 29 years with a range of 5-62 years. Overall, 21 cases (42%) had systemic disorders associated with intermediate uveitis and 29 cases (58%) had no associated systemic disease. A total of 11 patients (22%) had asthma, 4 (8%) had multiple sclerosis, 3 (6%) had presumed ocular tuberculosis, 1 (2%) had inflammatory bowel disease, 1 (2%) had non-Hodgkin lymphoma and 1 (2%) had sarcoidosis. Evidence of systemic disease was found in 50 (5%) of the 1,000 control subjects. Bronchial asthma was found in 37 patients (3.7 %), multiple sclerosis in 9 patients (0.9%), inflammatory bowel disease in 3 patients (0.3%), and tuberculosis in 1 patient (0.1%). None of the control patients had sarcoidosis or lymphoma. There were statistically significant associations between intermediate uveitis and bronchial asthma (p = 0.0001), multiple sclerosis (p = 0.003) and tuberculosis (p = 0.0005). Bronchial asthma and multiple sclerosis were the most frequently encountered systemic diseases associated with intermediate uveitis in our patient population. Patients with intermediate uveitis should undergo careful history-taking and investigations to rule out associated systemic illness.

  20. Higher order antibunching in intermediate states

    International Nuclear Information System (INIS)

    Verma, Amit; Sharma, Navneet K.; Pathak, Anirban

    2008-01-01

    Since the introduction of binomial state as an intermediate state, different intermediate states have been proposed. Different nonclassical effects have also been reported in these intermediate states. But till now higher order antibunching is predicted in only one type of intermediate state, which is known as shadowed negative binomial state. Recently we have shown that the higher order antibunching is not a rare phenomenon [P. Gupta, P. Pandey, A. Pathak, J. Phys. B 39 (2006) 1137]. To establish our earlier claim further, here we have shown that the higher order antibunching can be seen in different intermediate states, such as binomial state, reciprocal binomial state, hypergeometric state, generalized binomial state, negative binomial state and photon added coherent state. We have studied the possibility of observing the higher order subpoissonian photon statistics in different limits of intermediate states. The effects of different control parameters on the depth of non classicality have also been studied in this connection and it has been shown that the depth of nonclassicality can be tuned by controlling various physical parameters

  1. 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: phamhungviet@hus.edu.vn [Centre for Environmental Technology and Sustainable Development (CETASD), Hanoi University of Science, Nguyen Trai Street 334, Hanoi (Viet Nam); Hauser, Peter C., E-mail: Peter.Hauser@unibas.ch [University of Basel, Department of Chemistry, Spitalstrasse 51, Basel 4056 (Switzerland)

    2014-09-02

    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.

  2. Anaerobic Toxicity of Cationic Silver Nanoparticles

    Science.gov (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...

  3. Extraction and derivatization of chemical weapons convention relevant aminoalcohols on magnetic cation-exchange resins.

    Science.gov (United States)

    Singh, Varoon; Garg, Prabhat; Chinthakindi, Sridhar; Tak, Vijay; Dubey, Devendra Kumar

    2014-02-14

    Analysis and identification of nitrogen containing aminoalcohols is an integral part of the verification analysis of chemical weapons convention (CWC). This study was aimed to develop extraction and derivatization of aminoalcohols of CWC relevance by using magnetic dispersive solid-phase extraction (MDSPE) in combination with on-resin derivatization (ORD). For this purpose, sulfonated magnetic cation-exchange resins (SMRs) were prepared using magnetite nanoparticles as core, styrene and divinylbenzene as polymer coat and sulfonic acid as acidic cation exchanger. SMRs were successfully employed as extractant for targeted basic analytes. Adsorbed analytes were derivatized with hexamethyldisilazane (HMDS) on the surface of extractant. Derivatized (silylated) compounds were analyzed by GC-MS in SIM and full scan mode. The linearity of the method ranged from 5 to 200ngmL(-1). The LOD and LOQ ranged from 2 to 6ngmL(-1) and 5 to 19ngmL(-1) respectively. The relative standard deviation for intra-day repeatability and inter-day intermediate precision ranged from 5.1% to 6.6% and 0.2% to 7.6% respectively. Recoveries of analytes from spiked water samples from different sources varied from 28.4% to 89.3%. Copyright © 2014 Elsevier B.V. All rights reserved.

  4. Removal of radiocesium using cation exchange resin

    International Nuclear Information System (INIS)

    Morita-Murase, Yuko; Mizumura, Ryosuke; Tachibana, Yoshitaka; Kanazawa, Hideko

    2013-01-01

    Cation exchange resins (calcium polystyrene sulfonate, Ca-resin and sodium polystyrene sulfonate, Na-resin) have been used as agents to improve hyperkerlemia. For removing 137 Cs from the human body, the adsorption ability of the resin for 137 Cs was examined and evaluated. Resin (0.03 g) and 137 Cs (ca.1 kBq) were introduced into 3 mL of water, the Japanese Pharmacopoeia 1st fluid for a dissolution test (pH 1.2) and 2nd fluid (pH 6.8), respectively, and shaken. After 1-3 hours, the 137 Cs adsorption (%) of Na-resin was 99% in water, 60% in a pH 1.2 fluid and, 66% in a pH 6.8 fluid. By adding potassium, the 137 Cs adsorption (%) of Ca-resin was reduced. However, the 137 Cs adsorption (%) of Na-resin was almost unchanged. These results show that both resins have adsorption ability for 137 Cs in the stomach and the intestines. Therefore, the proposed method will be an effective means in the case of a radiological emergency due to 137 Cs. (author)

  5. Cyanide ion complexation by a cationic borane.

    Science.gov (United States)

    Chiu, Ching-Wen; Gabbaï, François P

    2008-02-14

    While we have previously reported that [1-(Mes2B)-8-(Me3NCH2)-C10H6]+ ([2]+) complexes fluoride ions to form [1-(Mes2FB)-8-(Me3NCH2)-C10H6] (2-F), we now show that this cationic borane also complexes cyanide to form [1-(Mes2(NC)B)-8-(Me3NCH2)-C10H6] (2-CN). This reaction also occurs under biphasic conditions (H2O-CHCl3) and may serve to transport cyanide in organic phases. The zwitterionic cyanoborate 2-CN has been fully characterized and its crystal structure determined. UV-vis titration experiments carried out in THF indicate that [2]+ has a higher affinity for fluoride (K > 10(8) M(-1)) than cyanide (K = 8.0 (+/-0.5) x 10(5) M(-1)). Steric effects which impede cyanide binding to the sterically congested boron center of [2]+ are most likely at the origin of this selectivity. Finally, electrochemical studies indicate that [2]+ is significantly more electrophilic than its neutral precursor 1-(Mes2B)-8-(Me2NCH2)-(C10H6) (1). These studies also show that reduction of [2]+ is irreversible, possibly because of elimination of the NMe3 moiety under reductive conditions. In fact, [2]OTf reacts with NaBH4 to afford 1-(Mes2B)-8-(CH3)-(C10H6) (4) which has also been fully characterized.

  6. Interaction of cationic drugs with liposomes.

    Science.gov (United States)

    Howell, Brett A; Chauhan, Anuj

    2009-10-20

    Interactions between cationic drugs and anionic liposomes were studied by measuring binding of drugs and the effect of binding on liposome permeability. The measurements were analyzed in the context of a continuum model based on electrostatic interactions and a Langmuir isotherm. Experiments and modeling indicate that, although electrostatic interactions are important, the fraction of drug sequestered in the double-layer is negligible. The majority of drug enters the bilayer with the charged regions interacting with the charged lipid head groups and the lipophilic regions associated with the bilayer. The partitioning of the drug can be described by a Langmuir isotherm with the electrostatic interactions increasing the sublayer concentration of the drug. The binding isotherms are similar for all tricyclic antidepressants (TCA). Bupivacaine (BUP) binds significantly less compared to TCA because its structure is such that the charged region has minimal interactions with the lipid heads once the BUP molecule partitions inside the bilayer. Conversely, the TCAs are linear with distinct hydrophilic and lipophilic regions, allowing the lipophilic regions to lie inside the bilayer and the hydrophilic regions to protrude out. This conformation maximizes the permeability of the bilayer, leading to an increased release of a hydrophilic fluorescent dye from liposomes.

  7. Radical Cations and Acid Protection during Radiolysis

    Energy Technology Data Exchange (ETDEWEB)

    Mincher, Bruce J. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Zarzana, Christopher A. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mezyk, Stephen P. [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2016-09-09

    Ligand molecules for used nuclear fuel separation schemes are exposed to high radiation fields and high concentrations of acid. Thus, an understanding of the complex interactions between extraction ligands, diluent, and acid is critical to understanding the performance of a separation process. The diglycolamides are ligands with important structural similarities to CMPO; however, previous work has shown that their radiolytic degradation has important mechanistic differences from CMPO. The DGAs do not enjoy radioprotection by HNO3 and the kinetics of DGA radiolytic degradation are different. CMPO degrades with pseudo-zero-order kinetics in linear fashion with absorbed dose while the DGAs degrade in pseudo-first-order, exponential fashion. This suggests that the DGAs degrade by simple reaction with some product of direct diluent radiolysis, while CMPO degradation is probably multi-step, with a slow step that is not dependent on the CMPO concentration, and mitigated by HNO3. It is thus believed that radio-protection and the zero-order radiolytic degradation kinetics are related, and that these phenomena are a function of either the formation of strong acid complexes with CMPO and/or to the presence of the CMPO phenyl ring. Experiments to test both these hypotheses have been designed and partially conducted. This report summarizes findings related to these phenomena for FY16, in satisfaction of milestone M3FT-16IN030104053. It also reports continued kinetic measurements for the reactions of the dodecane radical cation with solvent extraction ligands.

  8. Radical Cations and Acid Protection during Radiolysis

    International Nuclear Information System (INIS)

    Mincher, Bruce J.; Zarzana, Christopher A.; Mezyk, Stephen P.

    2016-01-01

    Ligand molecules for used nuclear fuel separation schemes are exposed to high radiation fields and high concentrations of acid. Thus, an understanding of the complex interactions between extraction ligands, diluent, and acid is critical to understanding the performance of a separation process. The diglycolamides are ligands with important structural similarities to CMPO; however, previous work has shown that their radiolytic degradation has important mechanistic differences from CMPO. The DGAs do not enjoy radioprotection by HNO3 and the kinetics of DGA radiolytic degradation are different. CMPO degrades with pseudo-zero-order kinetics in linear fashion with absorbed dose while the DGAs degrade in pseudo-first-order, exponential fashion. This suggests that the DGAs degrade by simple reaction with some product of direct diluent radiolysis, while CMPO degradation is probably multi-step, with a slow step that is not dependent on the CMPO concentration, and mitigated by HNO 3 . It is thus believed that radio-protection and the zero-order radiolytic degradation kinetics are related, and that these phenomena are a function of either the formation of strong acid complexes with CMPO and/or to the presence of the CMPO phenyl ring. Experiments to test both these hypotheses have been designed and partially conducted. This report summarizes findings related to these phenomena for FY16, in satisfaction of milestone M3FT-16IN030104053. It also reports continued kinetic measurements for the reactions of the dodecane radical cation with solvent extraction ligands.

  9. Riparian zone controls on base cation concentrations in boreal streams

    Science.gov (United States)

    Ledesma, J. L. J.; Grabs, T.; Futter, M. N.; Bishop, K. H.; Laudon, H.; Köhler, S. J.

    2013-01-01

    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.

  10. Stability of aqueous-alkaline sodium borohydride formulations

    International Nuclear Information System (INIS)

    Minkina, V.G.; Shabunya, S.I.; Kalinin, V.I.; Martynenko, V.V.

    2008-01-01

    Stability of sodium borohydride in the form of concentrated solutions and suspensions and solids corresponding to a crystal hydrate in composition was studied. The effects of temperature, concentrations of sodium borohydride and alkali, and nature of alkali metal cation on the rate of sodium borohydride hydrolysis were studied [ru

  11. Impact of monovalent cations on soil structure. Part II. Results of two Swiss soils

    Science.gov (United States)

    Farahani, Elham; Emami, Hojat; Keller, Thomas

    2018-01-01

    In this study, we investigated the impact of adding solutions with different potassium and sodium concentrations on dispersible clay, water retention characteristics, air permeability, and soil shrinkage behaviour using two agricultural soils from Switzerland with different clay content but similar organic carbon to clay ratio. Three different solutions (including only Na, only K, and the combination of both) were added to soil samples at three different cation ratio of soil structural stability levels, and the soil samples were incubated for one month. Our findings showed that the amount of readily dispersible clay increased with increasing Na concentrations and with increasing cation ratio of soil structural stability. The treatment with the maximum Na concentration resulted in the highest water retention and in the lowest shrinkage capacity. This was was associated with high amounts of readily dispersible clay. Air permeability generally increased during incubation due to moderate wetting and drying cycles, but the increase was negatively correlated with readily dispersible clay. Readily dispersible clay decreased with increasing K, while readily dispersible clay increased with increasing K in Iranian soil (Part I of our study). This can be attributed to the different clay mineralogy of the studied soils (muscovite in Part I and illite in Part II).

  12. Increased mineral oil bioavailability in slurries by monovalent cation-induced dispersion

    International Nuclear Information System (INIS)

    Jonge, H. de; Verstraten, J.M.

    1995-01-01

    Bioavailability of apolar contaminants is an important limiting factor for microbial reclamation of polluted soils. This paper describes a laboratory study of the relation between microaggregate stability and bioavailability of mineral oil in soil-water slurries. The stability of microaggregates in slurries is regulated by the valence and surface affinity of the cations in the system, and by the complexing anion P 2 O 7 4- (metaphosphate). A silt loam, contaminated with a weathered gas oil, was collected from an oil refinery site. Degradation rates were monitored in small-scale incubations at solid:liquid ratios of 1:5 (w/w). The solution contained Ca, Na, or K as the dominant cation. The levels of nutrients and metaphosphate were varied. Biodegradation rates increased with the sequence Ca 2 treatment. Measurements of the particle size distribution the slurry showed that an increase in the finer fractions qualitatively correlated with enhanced biodegradation. This is a strong indication that dispersion of the microaggregates increased bioavailability of the contaminant

  13. Cobalt(2) and nickel(2) tris-acetylacetonates with alkali metal cations in outer sphere

    International Nuclear Information System (INIS)

    Steblyanko, A.Yu.; Grigor'ev, A.N.; Martynenko, L.I.

    1996-01-01

    Anhydrous tris-acetylacetonates of Co(2) and Ni(2) with alkali metal cations in outer sphere were synthesized and investigated by different physicochemical methods. Chemical analysis and IR-spectroscopy show, that complex composition corresponds to the formula Eh[MA 3 ] (where Eh + - Li + , Na + , K + , Rb + , Cs + ; M - Co(2), Ni(2); A - - acetyacetonate-ion). Eh[MA 3 ] heating in vacuum leads to transition of volatile Co(2) and Ni(2) acetylacetonates to gaseous phase. The data of photoelectron spectroscopy and vacuum sublimation show, that Li[MA 3 ] is transformed to gaseous phase congruently and only partially dissociates to EhA and MA 2 . Li[MA 3 ] and Cs[MA 3 ] are characterized by the lowest thermal stability at atmospheric pressure. Low stability of Li[MA 3 ] is related with detachment of one of A - radical from [MA 3 ] complex anion by Li + cation under conditions, when LiA and Li[MA 3 ] are volatile. 11 refs.; 2 figs.; 3 tabs

  14. Effect of alkali metal cations on anodic dissolution of gold in cyanide solutions. Potentiodynamic measurement

    International Nuclear Information System (INIS)

    Bek, R.Yu.; Rogozhnikov, N.A.; Kosolapov, G.V.

    1998-01-01

    It is shown that gold dissolution rate in cyanic solutions in Li + , Na + , K + , Cs + cation series increases basically and decreases under cation concentration increasing. Cation effect on current value is caused by cations drawing in dense layer. A model of dense part of double layer with two Helmholtz planes (anion and cation) is suggested. Effect of nature and concentration of alkali metal cations on gold dissolution rate is explained on the base of the model [ru

  15. Preparation, characterization, and efficient transfection of cationic liposomes and nanomagnetic cationic liposomes

    Directory of Open Access Journals (Sweden)

    Samadikhah HR

    2011-10-01

    Full Text Available Hamid Reza Samadikhah1,*, Asia Majidi2,*, Maryam Nikkhah2, Saman Hosseinkhani11Department of Biochemistry, 2Department of Nanobiotechnology, Faculty of Biological Sciences, Tarbiat Modares University, Tehran, Iran *These authors contributed equally to this work Purpose: Cationic liposomes (CLs are composed of phospholipid bilayers. One of the most important applications of these particles is in drug and gene delivery. However, using CLs to deliver therapeutic nucleic acids and drugs to target organs has some problems, including low transfection efficiency in vivo. The aim of this study was to develop novel CLs containing magnetite to overcome the deficiencies. Patients and methods: CLs and magnetic cationic liposomes (MCLs were prepared using the freeze-dried empty liposome method. Luciferase-harboring vectors (pGL3 were transferred into liposomes and the transfection efficiencies were determined by luciferase assay. Firefly luciferase is one of most popular reporter genes often used to measure the efficiency of gene transfer in vivo and in vitro. Different formulations of liposomes have been used for delivery of different kinds of gene reporters. Lipoplex (liposome–plasmid DNA complexes formation was monitored by gel retardation assay. Size and charge of lipoplexes were determined using particle size analysis. Chinese hamster ovary cells were transfected by lipoplexes (liposome-pGL3; transfection efficiency and gene expression level was evaluated by luciferase assay. Results: High transfection efficiency of plasmid by CLs and novel nanomagnetic CLs was achieved. Moreover, lipoplexes showed less cytotoxicity than polyethyleneimine and Lipofectamine™. Conclusion: Novel liposome compositions (1,2-dipalmitoyl-sn-glycero-3-phosphocholine [DPPC]/dioctadecyldimethylammonium bromide [DOAB] and DPPC/cholesterol/DOAB with high transfection efficiency can be useful in gene delivery in vitro. MCLs can also be used for targeted gene delivery, due to

  16. Evaluation of phenomena affecting diffusion of cations in compacted bentonite

    International Nuclear Information System (INIS)

    Muurinen, A.; Lehikoinen, J.

    1995-04-01

    In a number of diffusion studies, contradictions between the apparent diffusivities of cations and their distribution coefficients in bentonite have been found. Two principal reasons have been offered as explanations for this discrepancy; diffusion of the sorbed cations, often called surface diffusion, and the decrease of sorption in compacted clay compared to a sorption value obtained from a batch experiment. In the study the information available from the literature on sorption-diffusion mechanisms of cations in bentonite has been compiled and re-interpreted in order to improve the understanding of the diffusion process. (103 refs., 23 figs., 8 tabs.)

  17. Microscopic theory of cation exchange in CdSe nanocrystals.

    Science.gov (United States)

    Ott, Florian D; Spiegel, Leo L; Norris, David J; Erwin, Steven C

    2014-10-10

    Although poorly understood, cation-exchange reactions are increasingly used to dope or transform colloidal semiconductor nanocrystals (quantum dots). We use density-functional theory and kinetic Monte Carlo simulations to develop a microscopic theory that explains structural, optical, and electronic changes observed experimentally in Ag-cation-exchanged CdSe nanocrystals. We find that Coulomb interactions, both between ionized impurities and with the polarized nanocrystal surface, play a key role in cation exchange. Our theory also resolves several experimental puzzles related to photoluminescence and electrical behavior in CdSe nanocrystals doped with Ag.

  18. Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism

    OpenAIRE

    Boughlala, Z.; Guerra, C.F.; Bickelhaupt, F.M.

    2016-01-01

    Abstract We have analyzed the structure and bonding of gas?phase Cl?X and [HCl?X]+ complexes for X+=?H+, CH3 +, Li+, and Na+, using relativistic density functional theory (DFT). We wish to establish a quantitative trend in affinities of the anionic and neutral Lewis bases Cl? and HCl for the various cations. The Cl?X bond becomes longer and weaker along X+?=?H+, CH3 +, Li+, and Na+. Our main purpose is to understand the heterolytic bonding mechanism behind the intrinsic (i.e., in the absence ...

  19. Application of remote sensing technique to site selection for low and intermediate level radioactive waste

    International Nuclear Information System (INIS)

    Chen Zhangru; Jin Yuanxin; Liu Yuemiao; Hou Dewen

    2001-01-01

    Based on the relative criteria of selection of disposal site for low and intermediate level radioactive waste, the social-economic conditions, landform, morphologic properties, regional geological stability, hydrogeological and engineering geological characters of adjacent area of Anhui, Zhejiang and Jiangsu provinces were investigated. The geological interpretation of thematic mapper images, field reconnaissance and data analysis were conducted during the research work. The results show that three areas in the west part of Zhejiang Province were recommended as potential site for disposal of low and intermediate level radioactive waste. They are Bajiaotang area, Tiebanchong area and Changxing-Guangde-Anji nabes

  20. Converting Hg-1212 to Tl-2212 via Tl-Hg cation exchange in combination with Tl cation intercalation

    International Nuclear Information System (INIS)

    Zhao Hua; Wu, Judy Z

    2007-01-01

    In a cation exchange process developed recently for epitaxy of HgBa 2 CaCu 2 O 6 (Hg-1212) thin films, TlBa 2 CaCu 2 O 7 (Tl-1212) or Tl 2 Ba 2 CaCu 2 O 9 (Tl-2212) precursor films were employed as the precursor matrices and Hg-1212 was obtained by replacing Tl cations on the precursor lattice with Hg cations. The reversibility of the cation exchange dictates directly the underlying mechanism. Following our recent success in demonstrating a complete reversibility within '1212' structure, we show the conversion from Hg-1212 to Tl-2212 can be achieved via two steps: conversion from Hg-1212 to Tl-1212 followed by Tl intercalation to form double Tl-O plans in each unit cell. The demonstrated reversibility of the cation exchange process has confirmed the process is a thermal perturbation of weakly bonded cations on the lattice and the direction of the process is determined by the population ratio between the replacing cations and that to be replaced

  1. Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds

    KAUST Repository

    Wang, Zhandong

    2017-11-28

    Decades of research on the autooxidation of organic compounds have provided fundamental and practical insights into these processes; however, the structure of many key autooxidation intermediates and the reactions leading to their formation still remain unclear. This work provides additional experimental evidence that highly oxygenated intermediates with one or more hydroperoxy groups are prevalent in the autooxidation of various oxygenated (e.g., alcohol, aldehyde, keto compounds, ether, and ester) and nonoxygenated (e.g., normal alkane, branched alkane, and cycloalkane) organic compounds. These findings improve our understanding of autooxidation reaction mechanisms that are routinely used to predict fuel ignition and oxidative stability of liquid hydrocarbons, while also providing insights relevant to the formation mechanisms of tropospheric aerosol building blocks. The direct observation of highly oxygenated intermediates for the autooxidation of alkanes at 500–600 K builds upon prior observations made in atmospheric conditions for the autooxidation of terpenes and other unsaturated hydrocarbons; it shows that highly oxygenated intermediates are stable at conditions above room temperature. These results further reveal that highly oxygenated intermediates are not only accessible by chemical activation but also by thermal activation. Theoretical calculations on H-atom migration reactions are presented to rationalize the relationship between the organic compound’s molecular structure (n-alkane, branched alkane, and cycloalkane) and its propensity to produce highly oxygenated intermediates via extensive autooxidation of hydroperoxyalkylperoxy radicals. Finally, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels.

  2. Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds

    KAUST Repository

    Wang, Zhandong; Popolan-Vaida, Denisia M.; Chen, Bingjie; Moshammer, Kai; Mohamed, Samah; Wang, Heng; Sioud, Salim; Raji, Misjudeen; Kohse-Hö inghaus, Katharina; Hansen, Nils; Dagaut, Philippe; Leone, Stephen R.; Sarathy, Mani

    2017-01-01

    Decades of research on the autooxidation of organic compounds have provided fundamental and practical insights into these processes; however, the structure of many key autooxidation intermediates and the reactions leading to their formation still remain unclear. This work provides additional experimental evidence that highly oxygenated intermediates with one or more hydroperoxy groups are prevalent in the autooxidation of various oxygenated (e.g., alcohol, aldehyde, keto compounds, ether, and ester) and nonoxygenated (e.g., normal alkane, branched alkane, and cycloalkane) organic compounds. These findings improve our understanding of autooxidation reaction mechanisms that are routinely used to predict fuel ignition and oxidative stability of liquid hydrocarbons, while also providing insights relevant to the formation mechanisms of tropospheric aerosol building blocks. The direct observation of highly oxygenated intermediates for the autooxidation of alkanes at 500–600 K builds upon prior observations made in atmospheric conditions for the autooxidation of terpenes and other unsaturated hydrocarbons; it shows that highly oxygenated intermediates are stable at conditions above room temperature. These results further reveal that highly oxygenated intermediates are not only accessible by chemical activation but also by thermal activation. Theoretical calculations on H-atom migration reactions are presented to rationalize the relationship between the organic compound’s molecular structure (n-alkane, branched alkane, and cycloalkane) and its propensity to produce highly oxygenated intermediates via extensive autooxidation of hydroperoxyalkylperoxy radicals. Finally, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels.

  3. Computational uncertainties in silicon dioxide/plutonium intermediate neutron spectrum systems

    International Nuclear Information System (INIS)

    Jaegers, P.J.

    1997-01-01

    In the past several years, several proposals have been made for the long-term stabilization and storage of surplus fissile materials. Many of these proposed scenarios involve systems that have an intermediate neutron energy spectrum. Such intermediate-energy systems are dominated by scattering and fission events induced by neutrons ranging in energy from 1 eV to 100keV. To ensure adequate safety margins and cost effectiveness, it is necessary to have benchmark data for these intermediate-energy spectrum systems; however, a review of the nuclear criticality benchmarks indicates that no formal benchmarks are available. Nuclear data uncertainties have been reported for some types of intermediate-energy spectrum systems. Using a variety of Monte Carlo computer codes and cross-section sets, reported significant variations in the calculated k ∞ of intermediate-energy spectrum metal/ 235 U systems. We discuss the characteristics of intermediate neutron spectrum systems and some of the computational differences that can occur in calculating the k eff of these systems

  4. Partially folded intermediates during trypsinogen denaturation

    Directory of Open Access Journals (Sweden)

    Martins N.F.

    1999-01-01

    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.

  5. Endomembrane Cation Transporters and Membrane Trafficking

    Energy Technology Data Exchange (ETDEWEB)

    Sze, Heven [Univ. of Maryland, College Park, MD (United States). Dept. of Cell Biology & Molecular Genetics

    2017-04-01

    Multicellular, as well as unicellular, organisms have evolved mechanisms to regulate ion and pH homeostasis in response to developmental cues and to a changing environment. The working hypothesis is that the balance of fluxes mediated by diverse transporters at the plasma membrane and in subcellular organelles determines ionic cellular distribution, which is critical for maintenance of membrane potential, pH control, osmolality, transport of nutrients, and protein activity. An emerging theme in plant cell biology is that cells respond and adapt to diverse cues through changes of the dynamic endomembrane system. Yet we know very little about the transporters that might influence the operation of the secretory system in plants. Here we focus on transporters that influence alkali cation and pH homeostasis, mainly in the endomembrane/ secretory system. The endomembrane system of eukaryote cells serves several major functions: i) sort cargo (e.g. enzymes, transporters or receptors) to specific destinations, ii) modulate the protein and lipid composition of membrane domains through remodeling, and iii) determine and alter the properties of the cell wall through synthesis and remodeling. We had uncovered a novel family of predicted cation/H+ exchangers (CHX) and K+ efflux antiporters (KEA) that are prevalent in higher plants, but rare in metazoans. We combined phylogenetic and transcriptomic analyses with molecular genetic, cell biological and biochemical studies, and have published the first reports on functions of plant CHXs and KEAs. CHX studied to date act at the endomembrane system where their actions are distinct from the better-studied NHX (Na/K-H+ exchangers). Arabidopsis thaliana CHX20 in guard cells modulate stomatal opening, and thus is significant for vegetative survival. Other CHXs ensure reproductive success on dry land, as they participate in organizing pollen walls, targeting of pollen tubes to the ovule or promoting

  6. Cation Coordination Alters the Conformation of a Thrombin-Binding G-Quadruplex DNA Aptamer That Affects Inhibition of Thrombin.

    Science.gov (United States)

    Zavyalova, Elena; Tagiltsev, Grigory; Reshetnikov, Roman; Arutyunyan, Alexander; Kopylov, Alexey

    2016-10-01

    Thrombin-binding aptamers are promising anticoagulants. HD1 is a monomolecular antiparallel G-quadruplex with two G-quartets linked by three loops. Aptamer-thrombin interactions are mediated with two TT-loops that bind thrombin exosite I. Several cations were shown to be coordinated inside the G-quadruplex, including K + , Na + , NH 4 + , Ba 2+ , and Sr 2+ ; on the contrary, Mn 2+ was coordinated in the grooves, outside the G-quadruplex. K + or Na + coordination provides aptamer functional activity. The effect of other cations on aptamer functional activity has not yet been described, because of a lack of relevant tests. Interactions between aptamer HD1 and a series of cations were studied. A previously developed enzymatic method was applied to evaluate aptamer inhibitory activity. The structure-function correlation was studied using the characterization of G-quadruplex conformation by circular dichroism spectroscopy. K + coordination provided the well-known high inhibitory activity of the aptamer, whereas Na + coordination supported low activity. Although NH 4 + coordination yielded a typical antiparallel G-quadruplex, no inhibitory activity was shown; a similar effect was observed for Ba 2+ and Sr 2+ coordination. Mn 2+ coordination destabilized the G-quadruplex that drastically diminished aptamer inhibitory activity. Therefore, G-quadruplex existence per se is insufficient for aptamer inhibitory activity. To elicit the nature of these effects, we thoroughly analyzed nuclear magnetic resonance (NMR) and X-ray data on the structure of the HD1 G-quadruplex with various cations. The most reasonable explanation is that cation coordination changes the conformation of TT-loops, affecting thrombin binding and inhibition. HD1 counterparts, aptamers 31-TBA and NU172, behaved similarly with some distinctions. In 31-TBA, an additional duplex module stabilized antiparallel G-quadruplex conformation at high concentrations of divalent cations; whereas in NU172, a different

  7. Metal Phosphates as Intermediate Temperature Proton Conducting Electrolytes

    DEFF Research Database (Denmark)

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

    2012-01-01

    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...... conductivity was observed under either a constant low water partial pressure or under a humidity cycling test within a period of more than 80 hours....

  8. Modeling linear and cyclic PKS intermediates through atom replacement.

    Science.gov (United States)

    Shakya, Gaurav; Rivera, Heriberto; Lee, D John; Jaremko, Matt J; La Clair, James J; Fox, Daniel T; Haushalter, Robert W; Schaub, Andrew J; Bruegger, Joel; Barajas, Jesus F; White, Alexander R; Kaur, Parminder; Gwozdziowski, Emily R; Wong, Fiona; Tsai, Shiou-Chuan; Burkart, Michael D

    2014-12-03

    The mechanistic details of many polyketide synthases (PKSs) remain elusive due to the instability of transient intermediates that are not accessible via conventional methods. Here we report an atom replacement strategy that enables the rapid preparation of polyketone surrogates by selective atom replacement, thereby providing key substrate mimetics for detailed mechanistic evaluations. Polyketone mimetics are positioned on the actinorhodin acyl carrier protein (actACP) to probe the underpinnings of substrate association upon nascent chain elongation and processivity. Protein NMR is used to visualize substrate interaction with the actACP, where a tetraketide substrate is shown not to bind within the protein, while heptaketide and octaketide substrates show strong association between helix II and IV. To examine the later cyclization stages, we extended this strategy to prepare stabilized cyclic intermediates and evaluate their binding by the actACP. Elongated monocyclic mimics show much longer residence time within actACP than shortened analogs. Taken together, these observations suggest ACP-substrate association occurs both before and after ketoreductase action upon the fully elongated polyketone, indicating a key role played by the ACP within PKS timing and processivity. These atom replacement mimetics offer new tools to study protein and substrate interactions and are applicable to a wide variety of PKSs.

  9. Macroeconomic stability

    DEFF Research Database (Denmark)

    Jespersen, Jesper

    2004-01-01

    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...

  10. Use of marker ion and cationic surfactant plastic membrane electrode for potentiometric titration of cationic polyelectrolytes.

    Science.gov (United States)

    Masadome, Takashi; Imato, Toshihiko

    2003-07-04

    A plasticized poly (vinyl chloride) (PVC) membrane electrode sensitive to stearyltrimethylammonium (STA) ion is applied to the determination of cationic polyelectrolytes such as poly (diallyldimethylammonium chloride) (Cat-floc) by potentiometric titration, using a potassium poly (vinyl sulfate) (PVSK) solution as a titrant. The end-point of the titration is detected as the potential change of the plasticized PVC membrane electrode caused by decrease in the concentration of STA ion added to the sample solution as a marker ion due to the ion association reaction between the STA ion and PVSK. The effects of the concentration of STA ion, coexisting electrolytes in the sample solution and pH of the sample on the degree of the potential change at the end-point were examined. A linear relationship between the concentration of cationic polyelectrolyte and the end-point volume of the titrant exists in the concentration range from 2x10(-5) to 4x10(-4) N for Cat-floc, glycol chitosan, and methylglycol chitosan.

  11. Opposing effects of cationic antimicrobial peptides and divalent cations on bacterial lipopolysaccharides

    Science.gov (United States)

    Smart, Matthew; Rajagopal, Aruna; Liu, Wing-Ki; Ha, Bae-Yeun

    2017-10-01

    The permeability of the bacterial outer membrane, enclosing Gram-negative bacteria, depends on the interactions of the outer, lipopolysaccharide (LPS) layer, with surrounding ions and molecules. We present a coarse-grained model for describing how cationic amphiphilic molecules (e.g., antimicrobial peptides) interact with and perturb the LPS layer in a biologically relevant medium, containing monovalent and divalent salt ions (e.g., Mg2+). In our approach, peptide binding is driven by electrostatic and hydrophobic interactions and is assumed to expand the LPS layer, eventually priming it for disruption. Our results suggest that in parameter ranges of biological relevance (e.g., at micromolar concentrations) the antimicrobial peptide magainin 2 effectively disrupts the LPS layer, even though it has to compete with Mg2+ for the layer. They also show how the integrity of LPS is restored with an increasing concentration of Mg2+. Using the approach, we make a number of predictions relevant for optimizing peptide parameters against Gram-negative bacteria and for understanding bacterial strategies to develop resistance against cationic peptides.

  12. Chemical bonding and structural ordering of cations in silicate glasses

    International Nuclear Information System (INIS)

    Calas, G.; Cormier, L.; Galoisy, L.; Ramos, A.; Rossano, St.

    1997-01-01

    The specific surrounding of cations in multicomponent silicate glasses is briefly presented. Information about interatomic distances and site geometry may be gained by using spectroscopic methods among which x-ray absorption spectroscopy may be used for the largest number of glass components. Scattering of x-rays and neutrons may also be used to determine the importance of medium range order around specific cations. All the existing data show that cations occur in sites with a well-defined geometry, which are in most cases connected to the silicate polymeric network. Medium range order has been detected around cations such as Ti, Ca and Ni, indicating that these elements have an heterogeneous distribution within the glassy matrix. (authors)

  13. Dynamics of photoexcited Ba+ cations in 4He nanodroplets

    International Nuclear Information System (INIS)

    2UB, Universitat de Barcelona, Diagonal 645, 08028 Barcelona (Spain))" data-affiliation=" (Departament ECM, Facultat de Física, and IN2UB, Universitat de Barcelona, Diagonal 645, 08028 Barcelona (Spain))" >Leal, Antonio; 2UB, Universitat de Barcelona, Diagonal 645, 08028 Barcelona (Spain))" data-affiliation=" (Departament ECM, Facultat de Física, and IN2UB, Universitat de Barcelona, Diagonal 645, 08028 Barcelona (Spain))" >Pi, Martí; Zhang, Xiaohang; Drabbels, Marcel; 2UB, Universitat de Barcelona, Diagonal 645, 08028 Barcelona (Spain); Laboratoire des Collisions, Agrégats, Réactivité, IRSAMC, UMR 5589, CNRS et Université Paul Sabatier-Toulouse 3, 118 route de Narbonne, F-31062 Toulouse Cedex 09 (France))" data-affiliation=" (Departament ECM, Facultat de Física, and IN2UB, Universitat de Barcelona, Diagonal 645, 08028 Barcelona (Spain); Laboratoire des Collisions, Agrégats, Réactivité, IRSAMC, UMR 5589, CNRS et Université Paul Sabatier-Toulouse 3, 118 route de Narbonne, F-31062 Toulouse Cedex 09 (France))" >Barranco, Manuel; Cargnoni, Fausto; Hernando, Alberto; Mateo, David; Mella, Massimo

    2016-01-01

    We present a joint experimental and theoretical study on the desolvation of Ba + cations in 4 He nanodroplets excited via the 6p ← 6s transition. The experiments reveal an efficient desolvation process yielding mainly bare Ba + cations and Ba + He n exciplexes with n = 1 and 2. The speed distributions of the ions are well described by Maxwell-Boltzmann distributions with temperatures ranging from 60 to 178 K depending on the excitation frequency and Ba + He n exciplex size. These results have been analyzed by calculations based on a time-dependent density functional description for the helium droplet combined with classical dynamics for the Ba + . In agreement with experiment, the calculations reveal the dynamical formation of exciplexes following excitation of the Ba + cation. In contrast to experimental observation, the calculations do not reveal desolvation of excited Ba + cations or exciplexes, even when relaxation pathways to lower lying states are included.

  14. Aggregation of trypsin and trypsin inhibitor by Al cation.

    Science.gov (United States)

    Chanphai, P; Kreplak, L; Tajmir-Riahi, H A

    2017-04-01

    Al cation may trigger protein structural changes such as aggregation and fibrillation, causing neurodegenerative diseases. We report the effect of Al cation on the solution structures of trypsin (try) and trypsin inhibitor (tryi), using thermodynamic analysis, UV-Visible, Fourier transform infrared (FTIR) spectroscopic methods and atomic force microscopy (AFM). Thermodynamic parameters showed Al-protein bindings occur via H-bonding and van der Waals contacts for trypsin and trypsin inhibitor. AFM showed that Al cations are able to force trypsin into larger or more robust aggregates than trypsin inhibitor, with trypsin 5±1 SE (n=52) proteins per aggregate and for trypsin inhibitor 8.3±0.7 SE (n=118). Thioflavin T test showed no major protein fibrillation in the presence of Al cation. Al complexation induced more alterations of trypsin inhibitor conformation than trypsin. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. Significant role of cationic polymers in drug delivery systems.

    Science.gov (United States)

    Farshbaf, Masoud; Davaran, Soodabeh; Zarebkohan, Amir; Annabi, Nasim; Akbarzadeh, Abolfazl; Salehi, Roya

    2017-11-06

    Cationic polymers are characterized as the macromolecules that possess positive charges, which can be either inherently in the polymer side chains and/or its backbone. Based on their origins, cationic polymers are divided in two category including natural and synthetic, in which the possessed positive charges are as result of primary, secondary or tertiary amine functional groups that could be protonated in particular situations. Cationic polymers have been employed commonly as drug delivery agents due to their superior encapsulation efficacy, enhanced bioavailability, low toxicity and improved release profile. In this paper, we focus on the most prominent examples of cationic polymers which have been revealed to be applicable in drug delivery systems and we also discuss their general synthesis and surface modification methods as well as their controlled release profile in drug delivery.

  16. Changing certain dietary cationic and anionic minerals: Impact on ...

    African Journals Online (AJOL)

    Changing certain dietary cationic and anionic minerals: Impact on blood chemistry, milk ... Increased blood pH and serum HCO3 were noticed in buffaloes fed with LC ... Serum calcium and chloride increased with decreased DCAD level while ...

  17. LABORATORY GAS-PHASE DETECTION OF THE CYCLOPROPENYL CATION (c-C{sub 3}H{sub 3} {sup +})

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Dongfeng; Doney, Kirstin D.; Linnartz, Harold, E-mail: zhao@strw.leidenuniv.nl [Sackler Laboratory for Astrophysics, Leiden Observatory, University of Leiden, PO Box 9513, NL 2300 RA Leiden (Netherlands)

    2014-08-20

    The cyclopropenyl cation (c-C{sub 3}H{sub 3} {sup +}) is the smallest aromatic hydrocarbon molecule and considered to be a pivotal intermediate in ion-molecule reactions in space. An astronomical identification has been prohibited so far, because of a lack of gas-phase data. Here we report the first high resolution infrared laboratory gas-phase spectrum of the ν {sub 4} (C-H asymmetric stretching) fundamental band of c-C{sub 3}H{sub 3} {sup +}. The c-C{sub 3}H{sub 3} {sup +} cations are generated in supersonically expanding planar plasma by discharging a propyne/helium gas pulse, yielding a rotational temperature of ∼35 K. The absorption spectrum is recorded in the 3.19 μm region using sensitive continuous-wave cavity ring-down spectroscopy. The analysis of about 130 ro-vibrational transitions results in precise spectroscopic parameters. These constants allow for an accurate comparison with high-level theoretical predictions, and provide the relevant information needed to search for this astrochemically relevant carbo-cation in space.

  18. The ARES High-level Intermediate Representation

    Energy Technology Data Exchange (ETDEWEB)

    Moss, Nicholas David [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-03-03

    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.

  19. Suppression of the two-dimensional electron gas in LaGaO3/SrTiO3 by cation intermixing

    KAUST Repository

    Nazir, S.

    2013-12-03

    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.

  20. Mercury release from deforested soils triggered by base cation enrichment

    International Nuclear Information System (INIS)

    Farella, N.; Lucotte, M.; Davidson, R.; Daigle, S.

    2006-01-01

    The Brazilian Amazon has experienced considerable colonization in the last few decades. Family agriculture based on slash-and-burn enables millions of people to live in that region. However, the poor nutrient content of most Amazonian soils requires cation-rich ashes from the burning of the vegetation biomass for cultivation to be successful, which leads to forest ecosystem degradation, soil erosion and mercury contamination. While recent studies have suggested that mercury present in soils was transferred towards rivers upon deforestation, little is known about the dynamics between agricultural land-use and mercury leaching. In this context, the present study proposes an explanation that illustrates how agricultural land-use triggers mercury loss from soils. This explanation lies in the competition between base cations and mercury in soils which are characterized by a low adsorption capacity. Since these soils are naturally very poor in base cations, the burning of the forest biomass suddenly brings high quantities of base cations to soils, destabilizing the previous equilibrium amongst cations. Base cation enrichment triggers mobility in soil cations, rapidly dislocating mercury atoms. This conclusion comes from principal component analyses illustrating that agricultural land-use was associated with base cation enrichment and mercury depletion. The overall conclusions highlight a pernicious cycle: while soil nutrient enrichment actually occurs through biomass burning, although on a temporary basis, there is a loss in Hg content, which is leached to rivers, entering the aquatic chain, and posing a potential health threat to local populations. Data presented here reflects three decades of deforestation activities, but little is known about the long-term impact of such a disequilibrium. These findings may have repercussions on our understanding of the complex dynamics of deforestation and agriculture worldwide