The microscopic Z-pinch process of current-carrying rarefied deuterium plasma shell

NASA Astrophysics Data System (ADS)

Ning, Cheng; Feng, Zhixing; Xue, Chuang; Li, Baiwen

2015-02-01

For insight into the microscopic mechanism of Z-pinch dynamic processes, a code of two-dimensional particle-in-cell (PIC) simulation has been developed in cylindrical coordinates. In principle, the Z-pinch of current-carrying rarefied deuterium plasma shell has been simulated by means of this code. Many results related to the microscopic processes of the Z-pinch are obtained. They include the spatio-temporal distributions of electromagnetic field, current density, forces experienced by the ions and electrons, positions and energy distributions of particles, and trailing mass and current. In radial direction, the electric and magnetic forces exerted on the electrons are comparable in magnitude, while the forces exerted on the ions are mainly the electric forces. So in the Z-pinch process, the electrons are first accelerated in Z direction and get higher velocities; then, they are driven inwards to the axis at the same time by the radial magnetic forces (i.e., Lorentz forces) of them. That causes the separations between the electrons and ions because the ion mass is much larger than the electron's, and in turn a strong electrostatic field is produced. The produced electrostatic field attracts the ions to move towards the electrons. When the electrons are driven along the radial direction to arrive at the axis, they shortly move inversely due to the static repellency among them and their tiny mass, while the ions continue to move inertially inwards, and later get into stagnation, and finally scatter outwards. Near the stagnation, the energies of the deuterium ions mostly range from 0.3 to 6 keV, while the electron energies are mostly from 5 to 35 keV. The radial components, which can contribute to the pinched plasma temperature, of the most probable energies of electron and ion at the stagnation are comparable to the Bennett equilibrium temperature (about 1 keV), and also to the highest temperatures of electron and ion obtained in one dimensional radiation magnetohydrodynamic simulation of the plasma shell Z-pinch. The trailing mass is about 20% of the total mass of the shell, and the maximum trailing current is about 7% of the driven current under our trailing definition. Our PIC simulation also demonstrates that the plasma shell first experiences a snow-plow like implosion process, which is relatively stable.

Coumarin-modified microporous-mesoporous Zn-MOF-74 showing ultra-high uptake capacity and photo-switched storage/release of U(VI) ions.

PubMed

Zhang, Le; Wang, Lin Lin; Gong, Le Le; Feng, Xue Feng; Luo, Ming Biao; Luo, Feng

2016-07-05

Driven by an energy crisis but consequently puzzled by various environmental problems, uranium, as the basic material of nuclear energy, is now receiving extensive attentions. In contrast to numerous sorbents applied in this field, metal-organic framework (MOFs), as a renovated material platform, has only recently been developed. How to improve the adsorption capacity of MOF materials towards U(VI) ions, as well as taking advantage of the nature of these MOFs to design photo-switched behaviour for photo-triggered storage/release of U(VI) ions are at present urgent problems and great challenges to be solved. Herein, we show a simple and facile method to target the goal. Through coordination-based post-synthetic strategy, microporous- mesoporous Zn-MOF-74 was easily functionalized by grafting coumarin on coordinatively unsaturated Zn(II) centers, yielding a series of coumarin-modified Zn-MOF-74 materials. The obtained samples displayed ultra-high adsorption capacity for U(VI) ions from water at pH value of 4 with maximum adsorption capacities as high as 360 mg/g (the record value in MOFs) and a remarkable photo-switched capability of 50 mg/g at pH value of 4. To the best of knowledge, and in contrast to the well-known photo-switched behaviour towards CO2, dye (propidium iodide), as well as fluorescence observed in MOFs, this is the first study that shows a photo-switched behaviour towards radioactive U(VI) ions in aqueous solution. Copyright © 2016 Elsevier B.V. All rights reserved.

Porphyrin coordination polymer nanospheres and nanorods

DOEpatents

Wang, Zhongchun; Shelnutt, John A.; Medforth, Craig J.

2012-12-04

A porphyrin coordination polymer nanostructure comprising a network of pyridyl porphyrin molecules and coordinating metal ions coordinatively bound through the pyridyl groups. In some embodiments, the porphyrins are metalloporphyrins. A variety of nanostructures are formed by the network polymer, including nanospheres, polygonal nanostructures, nanorods, and nanofibers, depending on a variety of factors including coordination metal ion, porphyrin type, metal of the metalloporphyrin, and degree of agitation during nanostructure formation. Reduction of coordinating metal ions may be used to form metal nanoparticles on the coordination polymer nanostructure.

Porphyrin coordination polymer nanospheres and nanorods

DOEpatents

Wang, Zhongchun; Shelnutt, John A.; Medforth, Craig J.

2013-09-10

A porphyrin coordination polymer nanostructure comprising a network of pyridyl porphyrin molecules and coordinating metal ions coordinatively bound through the pyridyl groups. In some embodiments, the porphyrins are metalloporphyrins. A variety of nanostructures are formed by the network polymer, including nanospheres, polygonal nanostructures, nanorods, and nanofibers, depending on a variety of factors including coordination metal ion, porphyrin type, metal of the metalloporphyrin, and degree of agitation during nanostructure formation. Reduction of coordinating metal ions may be used to form metal nanoparticles on the coordination polymer nanostructure.

Crystal structure of Helicobacter pylori neutrophil-activating protein with a di-nuclear ferroxidase center in a zinc or cadmium-bound form

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

Yokoyama, Hideshi, E-mail: h-yokoya@u-shizuoka-ken.ac.jp; Tsuruta, Osamu; Akao, Naoya

2012-06-15

Highlights: Black-Right-Pointing-Pointer Structures of a metal-bound Helicobacter pylori neutrophil-activating protein were determined. Black-Right-Pointing-Pointer Two zinc ions were tetrahedrally coordinated by ferroxidase center (FOC) residues. Black-Right-Pointing-Pointer Two cadmium ions were coordinated in a trigonal-bipyramidal and octahedral manner. Black-Right-Pointing-Pointer The second metal ion was more weakly coordinated than the first at the FOC. Black-Right-Pointing-Pointer A zinc ion was found in one negatively-charged pore suitable as an ion path. -- Abstract: Helicobacter pylori neutrophil-activating protein (HP-NAP) is a Dps-like iron storage protein forming a dodecameric shell, and promotes adhesion of neutrophils to endothelial cells. The crystal structure of HP-NAP in a Zn{sup 2+}-more » or Cd{sup 2+}-bound form reveals the binding of two zinc or two cadmium ions and their bridged water molecule at the ferroxidase center (FOC). The two zinc ions are coordinated in a tetrahedral manner to the conserved residues among HP-NAP and Dps proteins. The two cadmium ions are coordinated in a trigonal-bipyramidal and distorted octahedral manner. In both structures, the second ion is more weakly coordinated than the first. Another zinc ion is found inside of the negatively-charged threefold-related pore, which is suitable for metal ions to pass through.« less

Evidence of m = 1 density mode (plasma cam) in Saturn's rotating magnetosphere

NASA Astrophysics Data System (ADS)

Goldstein, J.; Waite, J. H.; Burch, J. L.; Livi, R.

2016-03-01

Cassini field and plasma data measured in the rotating Saturn Longitude System 3 (SLS3) coordinate system show positive evidence of structure whose dominant azimuthal wave number is m = 1: a long-lived, nonaxisymmetric, cam-shaped, global plasma distribution in Saturn's magnetosphere. Previous studies have identified evidence of this plasma cam in wave-derived electron density data and in Cassini Plasma Spectrometer (CAPS) W+ ion counts data. In this paper we report the first comprehensive analysis of CAPS ion moments data to identify the m = 1 density cam. We employ a multiyear, multispecies database of 685,678 CAPS density values, binned into a 1 RS by 4.8° discretized grid, spanning 4-19 RS. Fourier (harmonic) analysis shows that at most radial distances the dominant azimuthal mode is m = 1, for both W+ and H+ ion distributions. The majority (63%) of m = 1 ion peaks are clustered in an SLS3 quadrant centered at 330°. The plasma cam's existence has important implications for the global interchange-driven convection cycle and is a clue to solving the mystery of the rotational periodicities in Saturn's magnetosphere.

Polar Wind Measurements with TIDE/PSI and HYDRA on the Polar Spacecraft

NASA Technical Reports Server (NTRS)

Su, Y. J.; Horwitz, J. L.; Moore, Thomas E.; Giles, Barbara L.; Chandler, Michael O.; Craven, Paul D.; Chang, S.-W.; Scudder, J.

1998-01-01

The Thermal Ion Dynamics Experiment (TIDE) on the POLAR spacecraft has allowed sampling of the three-dimensional ion distributions with excellent energy, angular, and mass resolution. The companion Plasma Source Instrument, when operated, allows sufficient diminution of the electric potential to observe the polar wind at very high altitudes. In this presentation, we will describe the results of polar wind characteristics H+, He+, and 0+ as observed by TIDE at 5000 km and 8 RE altitudes. The relationship of the polar wind parameters with the solar zenith angle and with the day-night distance in the Solar Magnetic coordinate system will also be presented. We will compare these measurements with recent simulations of the photoelectron-driven polar wind using a couple fluid-semikinetic model. In addition, we will compare these polar wind observations with low-energy electrons sampled by the HYDRA experiment on POLAR to examine possible effects of the polar rain and photoelectrons and hopefully explain the large ion outflow velocity variations at POLAR apogee.

Acceleration of Ions and Electrons by Coronal Shocks

NASA Astrophysics Data System (ADS)

Sandroos, A.

2013-12-01

Diffusive shock acceleration (DSA) of particles at collisionless shock waves driven by coronal mass ejections (CMEs) is the best developed theory for the genesis of gradual solar energetic particle (SEP) events. According to DSA, particles scatter from fluctuations present in the ambient magnetic field, which causes some particles to encounter the shock front repeatedly and to gain energy during each crossing. DSA operating in solar corona is a complex process whose outcome depends on multiple parameters such as shock speed and strength, magnetic geometry, and composition of seed particles. Currently, STEREO and other near-Earth spacecraft are providing valuable multi-point information on how SEP properties, such as composition and energy spectra, vary in longitude. Initial results have shown that longitude distributions of large CME-associated SEP events are much wider than previously thought. These findings have many important consequences on SEP modeling. For example, it is important to extend the present models into two or three spatial coordinates to properly account for the effects of coronal and interplanetary magnetic geometry and the evolution of the CME-driven shock wave on the acceleration and transport of SEPs. We present a new model for the shock acceleration of ions and electrons in the solar corona and discuss implications for particle properties (energy spectra, longitudinal distribution, composition) in the resulting gradual SEP events. We also discuss the possible emission of type II radio waves by the accelerated coronal electrons. In the new model, the ion pitch angle scattering rate is calculated from modeled Alfvén wave power spectra using quasilinear theory. The energy gained by ions in scatterings are self-consistently removed from waves so that total energy (ions+waves) is conserved. New model has been implemented on massively parallel simulation platform Corsair.

Coordination Polymer Gels with Modular Nanomorphologies, Tunable Emissions, and Stimuli-Responsive Behavior Based on an Amphiphilic Tripodal Gelator.

PubMed

Sutar, Papri; Maji, Tapas Kumar

2017-08-21

The recent upsurge in research on coordination polymer gels (CPGs) stems from their synthetic modularity, nanoscale processability, and versatile functionalities. Here we report self-assembly of an amphiphilic, tripodal low-molecular weight gelator (L) that consists of 4,4',4-[1,3,5-phenyl-tri(methoxy)]-tris-benzene core and 2,2':6',2″-terpyridyl termini, with different metal ions toward the formation of CPGs that show controllable nanomorphologies, tunable emission, and stimuli-responsive behaviors. L can also act as a selective chemosensor for Zn II with very low limit of detection (0.18 ppm) in aqueous medium. Coordination-driven self-assembly of L with Zn II in H 2 O/MeOH solvent mixture results in a coordination polymer hydrogel (ZnL) that exhibits sheet like morphology and charge-transfer emission. On the other hand, coordination of L with Tb III and Eu III in CHCl 3 /tetrahydrofuran solvent mixture results in green- and red-emissive CPGs, respectively, with nanotubular morphology. Moreover, precise stoichiometric control of L/Eu III /Tb III ratio leads to the formation of bimetallic CPGs that show emissions over a broad spectral range, including white-light-emission. We also explore the multistimuli responsive properties of the white-light-emitting CPG by exploiting the dynamics of Ln III -tpy coordination.

Studies of ion kinetic effects in OMEGA shock-driven implosions using fusion burn imaging

NASA Astrophysics Data System (ADS)

Rosenberg, M. J.; Seguin, F. H.; Rinderknecht, H. G.; Sio, H.; Zylstra, A. B.; Gatu Johnson, M.; Frenje, J. A.; Li, C. K.; Petrasso, R. D.; Amendt, P. A.; Wilks, S. C.; Zimmerman, G.; Hoffman, N. M.; Kagan, G.; Molvig, K.; Glebov, V. Yu.; Stoeckl, C.; Marshall, F. J.; Seka, W.; Delettrez, J. A.; Sangster, T. C.; Betti, R.; Meyerhofer, D. D.; Atzeni, S.; Nikroo, A.

2014-10-01

Ion kinetic effects have been inferred in a series of shock-driven implosions at OMEGA from an increasing yield discrepancy between observations and hydrodynamic simulations as the ion-ion mean free path increases. To more precisely identify the nature and impact of ion kinetic effects, spatial burn profile measurements of DD and D3He reactions in these D3He-filled shock-driven implosions are presented and contrasted to both purely hydrodynamic models and models that include ion kinetic effects. It is shown that in implosions where the ion mean free path is equal to or greater than the size of the fuel region, purely hydrodynamic models fail to capture the observed burn profiles, while a model that includes ion diffusion is able to recover the observed burn profile shape. These results further elucidate the ion kinetic mechanisms that are present under long mean-free-path conditions after shock convergence in both shock-driven and ablatively-driven implosions. This work was supported in part by the U.S. DOE, NLUF, LLE, and LLNL.

Multivalent Ion Transport in Polymers via Metal-Ligand Coordination

NASA Astrophysics Data System (ADS)

Sanoja, Gabriel; Schauser, Nicole; Evans, Christopher; Majumdar, Shubhaditya; Segalman, Rachel

Elucidating design rules for multivalent ion conducting polymers is critical for developing novel high-performance materials for electrochemical devices. Herein, we molecularly engineer multivalent ion conducting polymers based on metal-ligand interactions and illustrate that both segmental dynamics and ion coordination kinetics are essential for ion transport through polymers. We present a novel statistical copolymer, poly(ethylene oxide-stat-imidazole glycidyl ether) (i.e., PEO-stat-PIGE), that synergistically combines the structural hierarchy of PEO with the Lewis basicity of tethered imidazole ligands (xIGE = 0.17) required to coordinate a series of transition metal salts containing bis(trifluoromethylsulfonyl)imide anions. Complexes of PEO-stat-PIGE with salts exhibit a nanostructure in which ion-enriched regions alternate with ion-deficient regions, and an ionic conductivity above 10-5 S/cm. Novel normalization schemes that account for ion solvation kinetics are presented to attain a universal scaling relationship for multivalent ion transport in polymers via metal-ligand coordination. AFOSR MURI program under FA9550-12-1.

Investigating the pharmacodynamic and magnetic properties of pyrophosphate-bridged coordination complexes

NASA Astrophysics Data System (ADS)

Ikotun, Oluwatayo (Tayo) F.

The multidentate nature of pyrophosphate makes it an attractive ligand for complexation of metal cations. The participation of pyrophosphate in a variety of biological pathways and its metal catalyzed hydrolysis has driven our investigation into its coordination chemistry. We have successfully synthesized a library of binuclear pyrophosphate bridge coordination complexes. The problem of pyrophosphate hydrolysis to phosphate in the presence of divalent metal ions was overcome by incorporating capping ligands such as 1,10-phenanthroline and 2,2'-bipyridine prior to the addition of the pyrophosphate. The magnetic properties of these complexes was investigated and magneto-structural analysis was conducted. The biological abundance of pyrophosphate and the success of metal based drugs such as cisplatin, prompted our investigation of the cytotoxic properties of M(II) pyrophosphate dimeric complexes (where M(II) is CoII, CuII, and NiII) in adriamycin resistant human ovarian cancer cells. Thess compounds were found to exhibit toxicity in the nanomolar to picomolar range. We conducted in vitro stability studies and the mechanism of cytoxicity was elucidated by performing DNA mobility and binding assays, enzyme inhibition assays, and in vitro oxidative stress studies.

Uranyl ion coordination

USGS Publications Warehouse

Evans, H.T.

1963-01-01

A review of the known crystal structures containing the uranyl ion shows that plane-pentagon coordination is equally as prevalent as plane-square or plane-hexagon. It is suggested that puckered-hexagon configurations of OH - or H2O about the uranyl group will tend to revert to plane-pentagon coordination. The concept of pentagonal coordination is invoked for possible explanations of the complex crystallography of the natural uranyl hydroxides and the unusual behavior of polynuclear ions in hydrolyzed uranyl solutions.

Metals in proteins: correlation between the metal-ion type, coordination number and the amino-acid residues involved in the coordination.

PubMed

Dokmanić, Ivan; Sikić, Mile; Tomić, Sanja

2008-03-01

Metal ions are constituents of many metalloproteins, in which they have either catalytic (metalloenzymes) or structural functions. In this work, the characteristics of various metals were studied (Cu, Zn, Mg, Mn, Fe, Co, Ni, Cd and Ca in proteins with known crystal structure) as well as the specificity of their environments. The analysis was performed on two data sets: the set of protein structures in the Protein Data Bank (PDB) determined with resolution <1.5 A and the set of nonredundant protein structures from the PDB. The former was used to determine the distances between each metal ion and its electron donors and the latter was used to assess the preferred coordination numbers and common combinations of amino-acid residues in the neighbourhood of each metal. Although the metal ions considered predominantly had a valence of two, their preferred coordination number and the type of amino-acid residues that participate in the coordination differed significantly from one metal ion to the next. This study concentrates on finding the specificities of a metal-ion environment, namely the distribution of coordination numbers and the amino-acid residue types that frequently take part in coordination. Furthermore, the correlation between the coordination number and the occurrence of certain amino-acid residues (quartets and triplets) in a metal-ion coordination sphere was analysed. The results obtained are of particular value for the identification and modelling of metal-binding sites in protein structures derived by homology modelling. Knowledge of the geometry and characteristics of the metal-binding sites in metalloproteins of known function can help to more closely determine the biological activity of proteins of unknown function and to aid in design of proteins with specific affinity for certain metals.

Synchronization and Random Triggering of Lymphatic Vessel Contractions

PubMed Central

Baish, James W.; Kunert, Christian; Padera, Timothy P.; Munn, Lance L.

2016-01-01

The lymphatic system is responsible for transporting interstitial fluid back to the bloodstream, but unlike the cardiovascular system, lacks a centralized pump-the heart–to drive flow. Instead, each collecting lymphatic vessel can individually contract and dilate producing unidirectional flow enforced by intraluminal check valves. Due to the large number and spatial distribution of such pumps, high-level coordination would be unwieldy. This leads to the question of how each segment of lymphatic vessel responds to local signals that can contribute to the coordination of pumping on a network basis. Beginning with elementary fluid mechanics and known cellular behaviors, we show that two complementary oscillators emerge from i) mechanical stretch with calcium ion transport and ii) fluid shear stress induced nitric oxide production (NO). Using numerical simulation and linear stability analysis we show that the newly identified shear-NO oscillator shares similarities with the well-known Van der Pol oscillator, but has unique characteristics. Depending on the operating conditions, the shear-NO process may i) be inherently stable, ii) oscillate spontaneously in response to random disturbances or iii) synchronize with weak periodic stimuli. When the complementary shear-driven and stretch-driven oscillators interact, either may dominate, producing a rich family of behaviors similar to those observed in vivo. PMID:27935958

Synchronization and Random Triggering of Lymphatic Vessel Contractions.

PubMed

Baish, James W; Kunert, Christian; Padera, Timothy P; Munn, Lance L

2016-12-01

The lymphatic system is responsible for transporting interstitial fluid back to the bloodstream, but unlike the cardiovascular system, lacks a centralized pump-the heart-to drive flow. Instead, each collecting lymphatic vessel can individually contract and dilate producing unidirectional flow enforced by intraluminal check valves. Due to the large number and spatial distribution of such pumps, high-level coordination would be unwieldy. This leads to the question of how each segment of lymphatic vessel responds to local signals that can contribute to the coordination of pumping on a network basis. Beginning with elementary fluid mechanics and known cellular behaviors, we show that two complementary oscillators emerge from i) mechanical stretch with calcium ion transport and ii) fluid shear stress induced nitric oxide production (NO). Using numerical simulation and linear stability analysis we show that the newly identified shear-NO oscillator shares similarities with the well-known Van der Pol oscillator, but has unique characteristics. Depending on the operating conditions, the shear-NO process may i) be inherently stable, ii) oscillate spontaneously in response to random disturbances or iii) synchronize with weak periodic stimuli. When the complementary shear-driven and stretch-driven oscillators interact, either may dominate, producing a rich family of behaviors similar to those observed in vivo.

Coinage metal complexes of 2-diphenylphosphino-3-methylindole.

PubMed

Koshevoy, Igor O; Shakirova, Julia R; Melnikov, Alexei S; Haukka, Matti; Tunik, Sergey P; Pakkanen, Tapani A

2011-08-21

Coordination of P,N indolyl-phosphine ligands to Au(I), Ag(I) and Cu(I) metal ions under weakly basic conditions results in easy deprotonation of the indolyl N-H function and effective formation of a family of homo- and heterobimetallic complexes MM'(PPh(2)C(9)H(7)N)(2) (M = M' = Au (2), Ag (5); M = Au, M' = Cu (3), Ag (4)). The latter (4) exists as an inseparable mixture of four different complexes, which are in equilibrium driven by slow dynamics. The reaction of silver(I) and copper(I) ions with PPh(2)(C(9)H(8)N) affords a rare tetranuclear Z-shaped cluster Ag(2)Cu(2)(PPh(2)C(9)H(7)N)(4) (6), which exhibits red luminescence in solid state (650 nm) and a weak dual emission in solution with the main component in the near-IR region (746 nm). This journal is © The Royal Society of Chemistry 2011

Statistical Determinants of Selective Ionic Complexation: Ions in Solvent, Transport Proteins, and Other “Hosts”

PubMed Central

Bostick, David L.; Brooks, Charles L.

2009-01-01

To provide utility in understanding the molecular evolution of ion-selective biomembrane channels/transporters, globular proteins, and ionophoric compounds, as well as in guiding their modification and design, we present a statistical mechanical basis for deconstructing the impact of the coordination structure and chemistry of selective multidentate ionic complexes. The deconstruction augments familiar ideas in liquid structure theory to realize the ionic complex as an open ion-ligated system acting under the influence of an “external field” provided by the host (or surrounding medium). Using considerations derived from this basis, we show that selective complexation arises from exploitation of a particular ion's coordination preferences. These preferences derive from a balance of interactions much like that which dictates the Hofmeister effect. By analyzing the coordination-state space of small family IA and VIIA ions in simulated fluid media, we derive domains of coordinated states that confer selectivity for a given ion upon isolating and constraining particular attributes (order parameters) of a complex comprised of a given type of ligand. We demonstrate that such domains may be used to rationalize the ion-coordinated environments provided by selective ionophores and biological ion channels/transporters of known structure, and that they can serve as a means toward deriving rational design principles for ion-selective hosts. PMID:19486671

Ion Selectivity in the KcsA Potassium Channel from the Perspective of the Ion Binding Site

PubMed Central

Dixit, Purushottam D.; Merchant, Safir; Asthagiri, D.

2009-01-01

To understand the thermodynamic exclusion of Na+ relative to K+ from the S2 site of the selectivity filter, the distribution PX(ɛ) (X = K+ or Na+) of the binding energy (ɛ) of the ion with the channel is analyzed using the potential distribution theorem. By expressing the excess chemical potential of the ion as a sum of mean-field 〈ɛ〉 and fluctuation μexflux,X contributions, we find that selectivity arises from a higher value of μflux,Na+ex relative to μflux,K+ex. To understand the role of site-site interactions on μexflux,X, we decompose PX(ɛ) into n-dependent distributions, where n is the number of ion-coordinating ligands within a distance λ from the ion. For λ comparable to typical ion-oxygen bond distances, investigations building on this multistate model reveal an inverse correlation between favorable ion-site and site-site interactions: the ion-coordination states that most influence the thermodynamics of the ion are also those for which the binding site is energetically less strained and vice versa. This correlation motivates understanding entropic effects in ion binding to the site and leads to the finding that μexflux,X is directly proportional to the average site-site interaction energy, a quantity that is sensitive to the chemical type of the ligand coordinating the ion. Increasing the coordination number around Na+ only partially accounts for the observed magnitude of selectivity; acknowledging the chemical type of the ion-coordinating ligand is essential. PMID:19289040

Solvent-coordinate free-energy landscape view of water-mediated ion-pair dissociation

NASA Astrophysics Data System (ADS)

Yonetani, Yoshiteru

2017-12-01

Water-mediated ion-pair dissociation is studied by molecular dynamics simulations of NaCl in water. Multidimensional free-energy analysis clarifies the relation between two essential solvent coordinates: the water coordination number and water-bridge formation. These two are related in a complex way. Both are necessary to describe ion-pair dissociation. The mechanism constructed with both solvent variables clearly shows the individual roles. The water coordination number is critical for starting ion-pair dissociation. Water-bridge formation is also important because it increases the likelihood of ion-pair dissociation by reducing the dissociation free-energy barrier. Additional Ca-Cl and NH4-Cl calculations show that these conclusions are unaffected by changes in the ion charge and shape. The present results will contribute to future explorations of many other molecular events such as surface water exchange and protein-ligand dissociation because the same mechanism is involved in such events.

Radiobiological study by using laser-driven proton beams

NASA Astrophysics Data System (ADS)

Yogo, A.; Sato, K.; Nishikino, M.; Mori, M.; Teshima, T.; Numasaki, H.; Murakami, M.; Demizu, Y.; Akagi, S.; Nagayama, S.; Ogura, K.; Sagisaka, A.; Orimo, S.; Nishiuchi, M.; Pirozhkov, A. S.; Ikegami, M.; Tampo, M.; Sakaki, H.; Suzuki, M.; Daito, I.; Oishi, Y.; Sugiyama, H.; Kiriyama, H.; Okada, H.; Kanazawa, S.; Kondo, S.; Shimomura, T.; Nakai, Y.; Tanoue, M.; Sugiyama, H.; Sasao, H.; Wakai, D.; Kawachi, T.; Nishimura, H.; Bolton, P. R.; Daido, H.

2009-07-01

Particle acceleration driven by high-intensity laser systems is widely attracting interest as a potential alternative to conventional ion acceleration, including ion accelerator applications to tumor therapy. Recent works have shown that a high intensity laser pulse can produce single proton bunches of a high current and a short pulse duration. This unique feature of laser-ion acceleration can lead to progress in the development of novel ion sources. However, there has been no experimental study of the biological effects of laser-driven ion beams. We describe in this report the first demonstrated irradiation effect of laser-accelerated protons on human lung cancer cells. In-vitro A549 cells are irradiated with a proton dose of 20 Gy, resulting in a distinct formation of γ-H2AX foci as an indicator of DNA double-strand breaks. This is a pioneering result that points to future investigations of the radiobiological effects of laser-driven ion beams. The laser-driven ion beam is apotential excitation source for time-resolved determination of hydroxyl (OH) radical yield, which will explore relationship between the fundamental chemical reactions of radiation effects and consequent biological processes.

Marcus Theory of Ion-Pairing

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

Roy, Santanu; Baer, Marcel D.; Mundy, Christopher J.

We present a theory for ion pair dissociation and association, motivated by the concepts of the Marcus theory of electron transfer. Despite the extensive research on ion-pairing in many chemical and biological processes, much can be learned from the exploration of collective reaction coordinates. To this end, we explore two reaction coordinates, ion pair distance and coordination number. The study of the correlation between these reaction coordinates provides a new insight into the mechanism and kinetics of ion pair dissociation and association in water. The potential of mean force on these 2D-surfaces computed from molecular dynamics simulations of different monovalentmore » ion pairs reveal a Marcus-like mechanism for ion-pairing: Water molecules rearrange forming an activated coordination state prior to ion pair dissociation or association, followed by relaxation of the coordination state due to further water rearrangement. Like Marcus theory, we find the existence of an inverted region where the transition rates are slower with increasing exergonicity. This study provides a new perspective for the future investigations of ion-pairing and transport. SR, CJM, and GKS were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. MDB was supported by MS3 (Materials Synthesis and Simulation Across Scales) Initiative, a Laboratory Directed Research and Development Program at Pacific Northwest National Laboratory (PNNL). The research was performed using PNNL Institutional Computing. PNNL is a multi-program national laboratory operated by Battelle for the U.S. Department of Energy.« less

A Bridge to Coordination Isomer Selection in Lanthanide(III) DOTA-tetraamide Complexes

PubMed Central

Vipond, Jeff; Woods, Mark; Zhao, Piyu; Tircso, Gyula; Ren, Jimin; Bott, Simon G.; Ogrin, Doug; Kiefer, Garry E.; Kovacs, Zoltan; Sherry, A.Dean

2008-01-01

Interest in macrocyclic lanthanide complexes such as DOTA is driven largely through interest in their use as contrast agents for MRI. The lanthanide tetraamide derivatives of DOTA have shown considerable promise as PARACEST agents, taking advantage of the slow water exchange kinetics of this class of complex. We postulated that water exchange in these tetraamide complexes could be slowed even further by introducing a group to sterically encumber the space above the water coordination site, thereby hindering the departure and approach of water molecules to the complex. The ligand 8O2-bridged-DOTAM was synthesized in a 34% yield from cyclen. It was found that the lanthanide complexes of this ligand did not possess a water molecule in the inner coordination sphere of the bound lanthanide. The crystal structure of the ytterbium complex revealed that distortions to the coordination sphere were induced by the steric constraints imposed on the complex by the bridging unit. The extent of the distortion was found to increase with increasing ionic radius of the lanthanide ion, eventually resulting in a complete loss of symmetry in the complex. Because this ligand system is bicyclic, the conformation of each ring in the system is constrained by that of the other, in consequence inclusion of the bridging unit in the complexes means only a twisted square antiprismatic coordination geometry is observed for complexes of 8O2-bridged-DOTAM. PMID:17295475

Laser-driven ion acceleration: methods, challenges and prospects

NASA Astrophysics Data System (ADS)

Badziak, J.

2018-01-01

The recent development of laser technology has resulted in the construction of short-pulse lasers capable of generating fs light pulses with PW powers and intensities exceeding 1021 W/cm2, and has laid the basis for the multi-PW lasers, just being built in Europe, that will produce fs pulses of ultra-relativistic intensities ~ 1023 - 1024 W/cm2. The interaction of such an intense laser pulse with a dense target can result in the generation of collimated beams of ions of multi-MeV to GeV energies of sub-ps time durations and of extremely high beam intensities and ion fluencies, barely attainable with conventional RF-driven accelerators. Ion beams with such unique features have the potential for application in various fields of scientific research as well as in medical and technological developments. This paper provides a brief review of state-of-the art in laser-driven ion acceleration, with a focus on basic ion acceleration mechanisms and the production of ultra-intense ion beams. The challenges facing laser-driven ion acceleration studies, in particular those connected with potential applications of laser-accelerated ion beams, are also discussed.

Uniform heating of materials into the warm dense matter regime with laser-driven quasimonoenergetic ion beams

DOE PAGES

Bang, W.; Albright, B. J.; Bradley, P. A.; ...

2015-12-01

In a recent experiment at the Trident laser facility, a laser-driven beam of quasimonoenergetic aluminum ions was used to heat solid gold and diamond foils isochorically to 5.5 and 1.7 eV, respectively. Here theoretical calculations are presented that suggest the gold and diamond were heated uniformly by these laser-driven ion beams. According to calculations and SESAME equation-of-state tables, laser-driven aluminum ion beams achievable at Trident, with a finite energy spread of ΔE/E~20%, are expected to heat the targets more uniformly than a beam of 140-MeV aluminum ions with zero energy spread. As a result, the robustness of the expected heatingmore » uniformity relative to the changes in the incident ion energy spectra is evaluated, and expected plasma temperatures of various target materials achievable with the current experimental platform are presented.« less

Uniform heating of materials into the warm dense matter regime with laser-driven quasimonoenergetic ion beams

NASA Astrophysics Data System (ADS)

Bang, W.; Albright, B. J.; Bradley, P. A.; Vold, E. L.; Boettger, J. C.; Fernández, J. C.

2015-12-01

In a recent experiment at the Trident laser facility, a laser-driven beam of quasimonoenergetic aluminum ions was used to heat solid gold and diamond foils isochorically to 5.5 and 1.7 eV, respectively. Here theoretical calculations are presented that suggest the gold and diamond were heated uniformly by these laser-driven ion beams. According to calculations and SESAME equation-of-state tables, laser-driven aluminum ion beams achievable at Trident, with a finite energy spread of ΔE /E ˜20 %, are expected to heat the targets more uniformly than a beam of 140-MeV aluminum ions with zero energy spread. The robustness of the expected heating uniformity relative to the changes in the incident ion energy spectra is evaluated, and expected plasma temperatures of various target materials achievable with the current experimental platform are presented.

Zn(II) and Hg(II) binding to a designed peptide that accommodates different coordination geometries.

PubMed

Szunyogh, Dániel; Gyurcsik, Béla; Larsen, Flemming H; Stachura, Monika; Thulstrup, Peter W; Hemmingsen, Lars; Jancsó, Attila

2015-07-28

Designed metal ion binding peptides offer a variety of applications in both basic science as model systems of more complex metalloproteins, and in biotechnology, e.g. in bioremediation of toxic metal ions, biomining or as artificial enzymes. In this work a peptide (HS: Ac-SCHGDQGSDCSI-NH2) has been specifically designed for binding of both Zn(II) and Hg(II), i.e. metal ions with different preferences in terms of coordination number, coordination geometry, and to some extent ligand composition. It is demonstrated that HS accommodates both metal ions, and the first coordination sphere, metal ion exchange between peptides, and speciation are characterized as a function of pH using UV-absorption-, synchrotron radiation CD-, (1)H-NMR-, and PAC-spectroscopy as well as potentiometry. Hg(II) binds to the peptide with very high affinity in a {HgS2} coordination geometry, bringing together the two cysteinates close to each end of the peptide in a loop structure. Despite the high affinity, Hg(II) is kinetically labile, exchanging between peptides on the subsecond timescale, as indicated by line broadening in (1)H-NMR. The Zn(II)-HS system displays more complex speciation, involving monomeric species with coordinating cysteinates, histidine, and a solvent water molecule, as well as HS-Zn(II)-HS complexes. In summary, the HS peptide displays conformational flexibility, contains many typical metal ion binding groups, and is able to accommodate metal ions with different structural and ligand preferences with high affinity. As such, the HS peptide may be a scaffold offering binding of a variety of metal ions, and potentially serve for metal ion sequestration in biotechnological applications.

Comparison between collective coordinate models for domain wall motion in PMA nanostrips in the presence of the Dzyaloshinskii-Moriya interaction

NASA Astrophysics Data System (ADS)

Vandermeulen, J.; Nasseri, S. A.; Van de Wiele, B.; Durin, G.; Van Waeyenberge, B.; Dupré, L.

2018-03-01

Lagrangian-based collective coordinate models for magnetic domain wall (DW) motion rely on an ansatz for the DW profile and a Lagrangian approach to describe the DW motion in terms of a set of time-dependent collective coordinates: the DW position, the DW magnetization angle, the DW width and the DW tilting angle. Another approach was recently used to derive similar equations of motion by averaging the Landau-Lifshitz-Gilbert equation without any ansatz, and identifying the relevant collective coordinates afterwards. In this paper, we use an updated version of the semi-analytical equations to compare the Lagrangian-based collective coordinate models with micromagnetic simulations for field- and STT-driven (spin-transfer torque-driven) DW motion in Pt/CoFe/MgO and Pt/Co/AlOx nanostrips. Through this comparison, we assess the accuracy of the different models, and provide insight into the deviations of the models from simulations. It is found that the lack of terms related to DW asymmetry in the Lagrangian-based collective coordinate models significantly contributes to the discrepancy between the predictions of the most accurate Lagrangian-based model and the micromagnetic simulations in the field-driven case. This is in contrast to the STT-driven case where the DW remains symmetric.

Langmuir-Blodgett deposition selects carboxylate headgroup coordination

NASA Astrophysics Data System (ADS)

Mukherjee, Smita; Datta, Alokmay

2011-10-01

Infrared reflection-absorption spectroscopy results on stearic acid Langmuir monolayers containing Mn, Co, and Cd ions show that on the water surface, the ions induce unidentate and bidentate (both chelate and bridged) coordination in the carboxylate headgroup with some trace of undissociated acid. Moreover, with Cd and Mn ions in subphase, the preferred coordination is found to be unidentate, whereas for Co, bidentate chelate is most preferred. After transfer onto amorphous substrate, not all coordinations are found to exist in the same ratio for the deposited metal stearate monolayers. More specifically, after transfer, Mn is found to coordinate with the carboxylate group as bidentate chelate, Cd as unidentate and bidentate bridged (with unidentate as the preferred coordination), and Co as preferably bidentate bridged (although all coordinations are present). Results suggest a specific interaction in each case, as the metal-carboxylate pair at the water surface is transferred to the substrate surface during Langmuir-Blodgett deposition.

N-donor co-ligands driven two new Co(II)- coordination polymers with bi- and trinuclear units: Crystal structures, and magnetic properties

NASA Astrophysics Data System (ADS)

Zhou, Zhi-Hang; Han, Min-Le; Wu, Ya-Pan; Dong, Wen-Wen; Li, Dong-Sheng; Lu, Jack Y.

2016-10-01

Two new Co(II) coordination polymers(CPs), namely [Co2(bpe)2(Hbppc)]n (1) and [Co3(μ3-OH)(bppc)(bpm)(H2O)]·3H2O (2) (H5bppc=biphenyl-2,4,6,3‧,5‧-pentacarboxylic acid, bpe=1,2-bis(4-pyridyl)ethene, bpm=bis(4-pyridyl)amine), have been obtained and characterized by elemental analysis, single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), IR spectra and thermogravimetric analysis (TGA). 1 shows a binodal (4,6)-connected fsc net with a (44·610·8)(44·62) topology, while 2 shows a binodal (5,7)-connected 3D network based on trinuclear [Co3(μ3-OH)]5+ units with unusual (3.46.52.6)(32.46.57.65.7) topology. Variable-temperature magnetic susceptibility measurements reveals that complex 1 shows ferromagnetic interactions between the adjacent Co(II) ions, whereas 2 is a antiferromagnetic system.

Numerical simulation of plasma processes driven by transverse ion heating

NASA Technical Reports Server (NTRS)

Singh, Nagendra; Chan, C. B.

1993-01-01

The plasma processes driven by transverse ion heating in a diverging flux tube are investigated with numerical simulation. The heating is found to drive a host of plasma processes, in addition to the well-known phenomenon of ion conics. The downward electric field near the reverse shock generates a doublestreaming situation consisting of two upflowing ion populations with different average flow velocities. The electric field in the reverse shock region is modulated by the ion-ion instability driven by the multistreaming ions. The oscillating fields in this region have the possibility of heating electrons. These results from the simulations are compared with results from a previous study based on a hydrodynamical model. Effects of spatial resolutions provided by simulations on the evolution of the plasma are discussed.

A Novel Coordination Polymer Constructed by Hetero-Metal Ions and 2,3-Pyridine Dicarboxylic Acid: Synthesis and Structure of [NiNa2(PDC)2(μ-H2O)(H2O)2] n

NASA Astrophysics Data System (ADS)

Dou, Ming-Yu; Lu, Jing

2017-12-01

A novel coordination polymer containing hetero-metal ions, [NiNa2(PDC)2(μ-H2O)(H2O)2] n , where PDC is 2,3-pyridine dicarboxylate ion, has been synthesized. In the structure, the PDC ligand chelates and bridges two Ni(II) and two Na(I) centers. Two kinds of metal centers are connected by μ4-PDC and μ2-H2O to form 2D coordination layers. Hydrogen bonds between coordination water molecules and carboxylate oxygen atoms further link these 2D coordination layers to form 3D supramolecular network.

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

Schreiber, J.; Max-Planck-Institut für Quantenoptik Garching, Hans-Kopfermann-Str. 1, 85748 Garching bei München; Bolton, P. R.

An overview of progress and typical yields from intense laser-plasma acceleration of ions is presented. The evolution of laser-driven ion acceleration at relativistic intensities ushers prospects for improved functionality and diverse applications which can represent a varied assortment of ion beam requirements. This mandates the development of the integrated laser-driven ion accelerator system, the multiple components of which are described. Relevant high field laser-plasma science and design of controlled optimum pulsed laser irradiation on target are dominant single shot (pulse) considerations with aspects that are appropriate to the emerging petawatt era. The pulse energy scaling of maximum ion energies andmore » typical differential spectra obtained over the past two decades provide guidance for continued advancement of laser-driven energetic ion sources and their meaningful applications.« less

Lanthanum(III) and Lutetium(III) in Nitrate-Based Ionic Liquids: A Theoretical Study of Their Coordination Shell.

PubMed

Bodo, Enrico

2015-09-03

By using ab initio molecular dynamics, we investigate the solvent shell structure of La(3+) and Lu(3+) ions immersed in two ionic liquids, ethylammonium nitrate (EAN) and its hydroxy derivative (2-ethanolammonium nitrate, HOEAN). We provide the first study of the coordination properties of these heavy metal ions in such a highly charged nonacqueous environment. We find, as expected, that the coordination in the liquid is mainly due to nitrate anions and that, due to the bidentate nature of the ligand, the complexation shell of the central ion has a nontrivial geometry and a coordination number in terms of nitrate molecules that apparently violates the decrease of ionic radii along the lanthanides series, since the smaller Lu(3+) ion seems to coordinate six nitrate molecules and the La(3+) ion only five. A closer inspection of the structural features obtained from our calculations shows, instead, that the first shell of oxygen atoms is more compact for Lu(3+) than for La(3+) and that the former coordinates 8 oxygen atoms while the latter 10 in accord with the typical lanthanide's trend along the series and that their first solvation shells have a slight irregular and complex geometrical pattern. When moving to the HOEAN solutions, we have found that the solvation of the central ion is possibly also due to the cation itself through the oxygen atom on the side chain. Also, in this liquid, the coordination numbers in terms of oxygen atoms in both solvents is 10 for La(3+) and 8 for Lu(3+).

Excitation of a nonlinear plasma ion wake by intense energy sources with applications to the crunch-in regime

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

Sahai, Aakash A.

We show the excitation of a nonlinear ion-wake mode by plasma electron modes in the bubble regime driven by intense energy sources, using analytical theory and simulations. The ion wake is shown to be a driven nonlinear ion-acoustic wave in the form of a long-lived cylindrical ion soliton which limits the repetition rate of a plasma-based particle accelerator in the bubble regime. We present the application of this evacuated and radially outwards propagating ion-wake channel with an electron skin-depth scale radius for the “crunch-in” regime of hollow-channel plasma. It is shown that the time-asymmetric focusing force phases in the bubblemore » couple to ion motion significantly differently than in the linear electron mode. The electron compression in the back of the bubble sucks in the ions whereas the space charge within the bubble cavity expels them, driving a cylindrical ion-soliton structure at the bubble radius. Once formed, the soliton is sustained and driven radially outwards by the thermal pressure of the wake energy in electrons. Particle-in-cell simulations are used to study the ion-wake soliton structure, its driven propagation and its use for positron acceleration in the crunch-in regime.« less

Excitation of a nonlinear plasma ion wake by intense energy sources with applications to the crunch-in regime

DOE PAGES

Sahai, Aakash A.

2017-08-23

We show the excitation of a nonlinear ion-wake mode by plasma electron modes in the bubble regime driven by intense energy sources, using analytical theory and simulations. The ion wake is shown to be a driven nonlinear ion-acoustic wave in the form of a long-lived cylindrical ion soliton which limits the repetition rate of a plasma-based particle accelerator in the bubble regime. We present the application of this evacuated and radially outwards propagating ion-wake channel with an electron skin-depth scale radius for the “crunch-in” regime of hollow-channel plasma. It is shown that the time-asymmetric focusing force phases in the bubblemore » couple to ion motion significantly differently than in the linear electron mode. The electron compression in the back of the bubble sucks in the ions whereas the space charge within the bubble cavity expels them, driving a cylindrical ion-soliton structure at the bubble radius. Once formed, the soliton is sustained and driven radially outwards by the thermal pressure of the wake energy in electrons. Particle-in-cell simulations are used to study the ion-wake soliton structure, its driven propagation and its use for positron acceleration in the crunch-in regime.« less

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

Wu, Jing-Yun, E-mail: jyunwu@ncnu.edu.tw; Tsai, Chi-Jou; Chang, Ching-Yun

A Zn(II)−salicylaldimine complex [Zn(L{sup salpyca})(H{sub 2}O)]{sub n} (1, where H{sub 2}L{sup salpyca}=4-hydroxy-3-(((pyridin-2-yl)methylimino)methyl)benzoic acid), with a one-dimensional (1D) chain structure, has been successfully converted to a discrete Ni(II)−salicylaldimine complex [Ni(L{sup salpyca})(H{sub 2}O){sub 3}] (2) and an infinite Cu(II)−salicylaldimine complex ([Cu(L{sup salpyca})]·3H{sub 2}O){sub n} (3) through a metal-ion exchange induced structural transformation process. However, such processes do not worked by Mn(II) and Co(II) ions. Solid-state structure analyses reveal that complexes 1–3 form comparable coordinative or supramolecular zigzag chains running along the crystallographic [201] direction. In addition, replacing Zn(II) ion by Ni(II) and Cu(II) ions caused changes in coordination environment and sphere ofmore » metal centers, from a 5-coordinate intermediate geometry of square pyramidal and trigonal bipyramidal in 1 to a 6-coordinate octahedral geometry in 2, and to a 4-coordiante square planar geometry in 3. This study shows that metal-ion exchange serves as a very efficient way of forming new coordination complexes that may not be obtained through direct synthesis. - Graphical abstract: A Zn(II)−salicylaldimine zigzag chain has been successfully converted to a Ni(II)−salicylaldimine supramolecular zigzag chain and a Cu(II)−salicylaldimine coordinative zigzag chain through metal-ion exchange induced structural transformations, which is not achieved by Mn(II) and Co(II) ions.« less

Selective complexation of K+ and Na+ in simple polarizable ion-ligating systems.

PubMed

Bostick, David L; Brooks, Charles L

2010-09-29

An influx of experimental and theoretical studies of ion transport protein structure has inspired efforts to understand underlying determinants of ionic selectivity. Design principles for selective ion binding can be effectively isolated and interrogated using simplified models composed of a single ion surrounded by a set of ion-ligating molecular species. While quantum mechanical treatments of such systems naturally incorporate electronic degrees of freedom, their computational overhead typically prohibits thorough dynamic sampling of configurational space and, thus, requires approximations when determining ion-selective free energy. As an alternative, we employ dynamical simulations with a polarizable force field to probe the structure and K(+)/Na(+) selectivity in simple models composed of one central K(+)/Na(+) ion surrounded by 0-8 identical model compounds: N-methylacetamide, formamide, or water. In the absence of external restraints, these models represent gas-phase clusters displaying relaxed coordination structures with low coordination number. Such systems display Na(+) selectivity when composed of more than ∼3 organic carbonyl-containing compounds and always display K(+) selectivity when composed of water molecules. Upon imposing restraints that solely enforce specific coordination numbers, we find all models are K(+)-selective when ∼7-8-fold ion coordination is achieved. However, when models composed of the organic compounds provide ∼4-6-fold coordination, they retain their Na(+) selectivity. From these trends, design principles emerge that are of basic importance in the behavior of K(+) channel selectivity filters and suggest a basis not only for K(+) selectivity but also for modulation of block and closure by smaller ions.

Higher order Larmor radius corrections to guiding-centre equations and application to fast ion equilibrium distributions

NASA Astrophysics Data System (ADS)

Lanthaler, S.; Pfefferlé, D.; Graves, J. P.; Cooper, W. A.

2017-04-01

An improved set of guiding-centre equations, expanded to one order higher in Larmor radius than usually written for guiding-centre codes, are derived for curvilinear flux coordinates and implemented into the orbit following code VENUS-LEVIS. Aside from greatly improving the correspondence between guiding-centre and full particle trajectories, the most important effect of the additional Larmor radius corrections is to modify the definition of the guiding-centre’s parallel velocity via the so-called Baños drift. The correct treatment of the guiding-centre push-forward with the Baños term leads to an anisotropic shift in the phase-space distribution of guiding-centres, consistent with the well-known magnetization term. The consequence of these higher order terms are quantified in three cases where energetic ions are usually followed with standard guiding-centre equations: (1) neutral beam injection in a MAST-like low aspect-ratio spherical equilibrium where the fast ion driven current is significantly larger with respect to previous calculations, (2) fast ion losses due to resonant magnetic perturbations where a lower lost fraction and a better confinement is confirmed, (3) alpha particles in the ripple field of the European DEMO where the effect is found to be marginal.

Mathematical model reveals role of nucleotide signaling in airway surface liquid homeostasis and its dysregulation in cystic fibrosis

PubMed Central

Sandefur, Conner I.; Boucher, Richard C.; Elston, Timothy C.

2017-01-01

Mucociliary clearance is composed of three components (i.e., mucin secretion, airway surface hydration, and ciliary-activity) which function coordinately to clear inhaled microbes and other foreign particles from airway surfaces. Airway surface hydration is maintained by water fluxes driven predominantly by active chloride and sodium ion transport. The ion channels that mediate electrogenic ion transport are regulated by extracellular purinergic signals that signal through G protein-coupled receptors. These purinoreceptors and the signaling pathways they activate have been identified as possible therapeutic targets for treating lung disease. A systems-level description of airway surface liquid (ASL) homeostasis could accelerate development of such therapies. Accordingly, we developed a mathematical model to describe the dynamic coupling of ion and water transport to extracellular purinergic signaling. We trained our model from steady-state and time-dependent experimental measurements made using normal and cystic fibrosis (CF) cultured human airway epithelium. To reproduce CF conditions, reduced chloride secretion, increased potassium secretion, and increased sodium absorption were required. The model accurately predicted ASL height under basal normal and CF conditions and the collapse of surface hydration due to the accelerated nucleotide metabolism associated with CF exacerbations. Finally, the model predicted a therapeutic strategy to deliver nucleotide receptor agonists to effectively rehydrate the ASL of CF airways. PMID:28808008

catena-Poly[[(benzil bis{[(pyridin-2-yl)methylidene]hydrazone}-κ⁴N,N',N'',N''')mercury(II)]-μ-chlorido-[dichloridomercury(II)]-μ-chlorido].

PubMed

Akkurt, Mehmet; Khandar, Ali Akbar; Tahir, Muhammad Nawaz; Hosseini-Yazdi, Seyed Abolfazl; Mahmoudi, Ghodrat

2012-07-01

In the title coordination polymer, [Hg₄Cl₄(C₂₆H₂₀N₆)](n), one Hg(II) ion is coordinated by four N atoms from the benzylbis((pyridin-2-yl)methyl-idenehydrazone) ligand and two Cl⁻ ions in a very distorted cis-HgCl₂N₄ octa-hedral geometry. The other Hg(II) ion is coordinated in a distorted tetra-hedral geometry by four Cl⁻ ions. Bridging chloride ions link the Hg(II) ions into a chain propagating in [010]: the Hg-Cl bridging bonds are significantly longer than the terminal bonds. The dihedral angle between the central benzene rings of the ligand is 83.3 (2)°. The packing is consolidated by weak C-H⋯Cl hydrogen bonds and C-H⋯π inter-actions.

Ion energy spread and current measurements of the rf-driven multicusp ion source

NASA Astrophysics Data System (ADS)

Lee, Y.; Gough, R. A.; Kunkel, W. B.; Leung, K. N.; Perkins, L. T.; Pickard, D. S.; Sun, L.; Vujic, J.; Williams, M. D.; Wutte, D.

1997-03-01

Axial energy spread and useful beam current of positive ion beams have been carried out using a radio frequency (rf)-driven multicusp ion source. Operating the source with a 13.56 MHz induction discharge, the axial energy spread is found to be approximately 3.2 eV. The extractable beam current of the rf-driven source is found to be comparable to that of filament-discharge sources. With a 0.6 mm diameter extraction aperture, a positive hydrogen ion beam current density of 80 mA/cm2 can be obtained at a rf input power of 2.5 kW. The expected source lifetime is much longer than that of filament discharges.

Coordinating properties of uridine 5'-monophosphate with selected Ln(3+) ions in ionic micellar media.

PubMed

Sudhiranjan Singh, M; Homendra, Naorem; Lonibala, R K

2012-12-01

Coordinating properties of uridine 5'-monophosphate (UMP) towards trivalent La, Pr, Nd, Sm, Eu and Gd ions in presence of cationic and anionic micelles have been investigated by potentiometric pH-titration and spectroscopic methods. Stability constants of the 2:1 complexes have been determined and the change in free energy, enthalpy and entropy associated with the complexation are also calculated. Nd(III) complexes isolated from aqueous and aqueous-micellar media do not show any significant structural difference. Formation of Ln(III) complexes in all cases completes below pH 7.5 showing that UMP best interacts with Ln(3+) ions at the physiological pH range 7.3-7.5. The nucleobase is not involved in the complexation and the metal ion coordination of UMP is through the phosphate moiety only. Coordinating tendency of UMP with lanthanides, Nd(III) ion in particular, at different pH is also discussed. Luminescent properties of Eu(III) complex and its decay lifetime are also presented. This information may prove helpful regarding the use of lanthanides as biological probes for calcium/magnesium ions.

UV-light-driven prebiotic synthesis of iron-sulfur clusters

NASA Astrophysics Data System (ADS)

Bonfio, Claudia; Valer, Luca; Scintilla, Simone; Shah, Sachin; Evans, David J.; Jin, Lin; Szostak, Jack W.; Sasselov, Dimitar D.; Sutherland, John D.; Mansy, Sheref S.

2017-12-01

Iron-sulfur clusters are ancient cofactors that play a fundamental role in metabolism and may have impacted the prebiotic chemistry that led to life. However, it is unclear whether iron-sulfur clusters could have been synthesized on prebiotic Earth. Dissolved iron on early Earth was predominantly in the reduced ferrous state, but ferrous ions alone cannot form polynuclear iron-sulfur clusters. Similarly, free sulfide may not have been readily available. Here we show that UV light drives the synthesis of [2Fe-2S] and [4Fe-4S] clusters through the photooxidation of ferrous ions and the photolysis of organic thiols. Iron-sulfur clusters coordinate to and are stabilized by a wide range of cysteine-containing peptides and the assembly of iron-sulfur cluster-peptide complexes can take place within model protocells in a process that parallels extant pathways. Our experiments suggest that iron-sulfur clusters may have formed easily on early Earth, facilitating the emergence of an iron-sulfur-cluster-dependent metabolism.

Coordinated Polar Spacecraft, Geosynchronous Spacecraft, and Ground-based Observations of Magnetopause Oscillations and Pc5 Waves in the Magnetosphere

NASA Technical Reports Server (NTRS)

Le, G.; Chen, S.; Zheng, Y.; Russell, C. T.; Slavin, J. A.; Huang, C.-S.; Petrinec, S. S.; Moore, T. E.; Samson, J.; Singer, H. J.

2005-01-01

In this paper, we present in situ observations of surface waves at the magnetopause and oscillatory magnetospheric field lines, and coordinated observations Pc5 waves at geosynchronous orbit by the GOES spacecraft, and on the ground by CANOPUS and 210 Degree Magnetic Meridian (210MMJ magnetometer arrays. On February 7,2002 during a highspeed solar wind stream, the Polar spacecraft was skimming the magnetopause in a post-noon meridian plane for approximately 3 hours. During this interval, it made two short excursions and a few partial crossings into the magnetosheath and observed quasi-periodic cold ion bursts in the region adjacent to the magnetopause current layer. The multiple magnetopause crossings as well as the velocity of the cold ion bursts indicate that the magnetopause was oscillating with about 6 minute period. Simultaneous observations of Pc5 waves at geosynchronous orbit by the GOES spacecraft and on the ground by the CANOPUS magnetometer array reveal that these magnetospheric pulsations were forced oscillations of magnetic field lines directly driven by the magnetopause oscillations. The magnetospheric pulsations occurred only in a limited longitudinal region in the post-noon dayside sector, and were not a global phenomenon as one would expect for global field line resonance. Thus, the magnetopause oscillations at the source were also limited to a localized region spanning about 4 hours in local time.

Assembly and Properties of Heterobimetallic CoII/III/CaII Complexes with Aquo and Hydroxo Ligands

PubMed Central

Lacy, David C.; Park, Young Jun; Ziller, Joseph W.; Yano, Junko; Borovik, A. S.

2012-01-01

The use of water as a reagent in redox-driven reactions is advantageous because it is abundant and environmentally compatible. The conversion of water to dioxygen in photosynthesis illustrates one example, in which a redox-inactive CaII ion and four manganese ions are required for function. In this report we describe the stepwise formation of two new heterobimetallic complexes containing CoII/III and CaII ions, and either hydroxo or aquo ligands. The preparation of a 4-coordinate CoII synthon was achieved with the tripodal ligand, N,N′,N″-[2,2′,2″-nitrilotris(ethane-2,1-diyl)]tris(2,4,6-trimethylbenzenesulfonamido, [MST]3−. Water binds to [CoIIMST]− to form the 5-coordinate [CoIIMST(OH2)]− complex that was used to prepare the CoII/CaII complex [CoIIMST(μ-OH2)CaII⊂15-crown-5(OH2)]+ ([CoII(μ-OH2)CaIIOH2]+). [CoII(μ-OH2)CaOH2]+ contained two aquo ligands, one bonded to the CaII ion and one bridging between the two metal ions and thus represents an unusual example of a heterobimetallic complex containing 2 aquo ligands spanning different metal ions. Both aquo ligands formed intramolecular hydrogen bonds with the [MST]3− ligand. [CoIIMST(OH2)]− was oxidized to form [CoIIIMST(OH2)] that was further converted to [CoIIIMST(μ-OH)CaII⊂15-crown-5]+ ([CoIII(μ-OH)CaII]+) in the presence of base and CaIIOTf2/15-crown-5. [CoIII(μ-OH)CaII]+ was also synthesized from the oxidation of [CoIIMST]− with PhIO in the presence of CaIIOTf2/15-crown-5. Allowing [CoIII(μ-OH)CaII]+ to react with diphenylhydrazine afforded [CoII(μ-OH2)CaIIOH2]+ and azobenzene. Additionally, the characterization of [CoIII(μ-OH)CaII]+ provides another formulation for the previously reported CoIV–oxo complex, [(TMG3tren)CoIV(μ-O)ScIII(OTf)3]2+ to one that instead could contain a CoIII–OH unit. PMID:22998407

Facial and meridional isomers of holmium-nitrate N-tert-butylacetamide complexes

NASA Astrophysics Data System (ADS)

Chang, Ye-Di; Xue, Jun-Hui; Kang, Xiao-Yan; Yang, Li-Min; Li, Wei-Hong; Xu, Yi-Zhuang; Zhao, Guo-Zhong; Zhang, Gao-Hui; Liu, Ke-Xin; Chen, Jia-Er; Wu, Jin-Guang

2018-06-01

Two Ho(C6H13NO)3(NO3)3 complexes formed by holmium nitrate and N-tert-butylacetamide (NtBA) (Ho-NtBA(I) in a Cc space group, and Ho-NtBA(II) in a P21/c space group) are reported here to investigate the coordination of lanthanide ions with amide groups. Using X-ray single crystal diffraction, FTIR, Raman, FIR and THz methods the structures of the two complexes were identified, in which Ho3+ is 9-coordinated to three carbonyl oxygen atoms provided by three NtBA ligands and three bidentate nitrate ions to form the "facial" and "meridional" isomers. Their FTIR and Raman spectra indicate the formation of two holmium complexes, the variations of NtBA after holmium coordination and the spectra are similar for the isomers in some extent. Their FIR and THz spectroscopic results show the coordination of holmium ions and THz maybe more sensitive to isomers. The results demonstrate the coordination behaviors of holmium ions and NtBA ligand.

A Study of the Hydration of the Alkali Metal Ions in Aqueous Solution

PubMed Central

2011-01-01

The hydration of the alkali metal ions in aqueous solution has been studied by large angle X-ray scattering (LAXS) and double difference infrared spectroscopy (DDIR). The structures of the dimethyl sulfoxide solvated alkali metal ions in solution have been determined to support the studies in aqueous solution. The results of the LAXS and DDIR measurements show that the sodium, potassium, rubidium and cesium ions all are weakly hydrated with only a single shell of water molecules. The smaller lithium ion is more strongly hydrated, most probably with a second hydration shell present. The influence of the rubidium and cesium ions on the water structure was found to be very weak, and it was not possible to quantify this effect in a reliable way due to insufficient separation of the O–D stretching bands of partially deuterated water bound to these metal ions and the O–D stretching bands of the bulk water. Aqueous solutions of sodium, potassium and cesium iodide and cesium and lithium hydroxide have been studied by LAXS and M–O bond distances have been determined fairly accurately except for lithium. However, the number of water molecules binding to the alkali metal ions is very difficult to determine from the LAXS measurements as the number of distances and the temperature factor are strongly correlated. A thorough analysis of M–O bond distances in solid alkali metal compounds with ligands binding through oxygen has been made from available structure databases. There is relatively strong correlation between M–O bond distances and coordination numbers also for the alkali metal ions even though the M–O interactions are weak and the number of complexes of potassium, rubidium and cesium with well-defined coordination geometry is very small. The mean M–O bond distance in the hydrated sodium, potassium, rubidium and cesium ions in aqueous solution have been determined to be 2.43(2), 2.81(1), 2.98(1) and 3.07(1) Å, which corresponds to six-, seven-, eight- and eight-coordination. These coordination numbers are supported by the linear relationship of the hydration enthalpies and the M–O bond distances. This correlation indicates that the hydrated lithium ion is four-coordinate in aqueous solution. New ionic radii are proposed for four- and six-coordinate lithium(I), 0.60 and 0.79 Å, respectively, as well as for five- and six-coordinate sodium(I), 1.02 and 1.07 Å, respectively. The ionic radii for six- and seven-coordinate K+, 1.38 and 1.46 Å, respectively, and eight-coordinate Rb+ and Cs+, 1.64 and 1.73 Å, respectively, are confirmed from previous studies. The M–O bond distances in dimethyl sulfoxide solvated sodium, potassium, rubidium and cesium ions in solution are very similar to those observed in aqueous solution. PMID:22168370

Combining Jaynes-Cummings and anti-Jaynes-Cummings dynamics in a trapped-ion system driven by a laser

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

Rodriguez-Lara, B.M.; Moya-Cessa, H.; Klimov, A.B.

2005-02-01

We show that, if one combines the Jaynes-Cummings and anti-Jaynes-Cummings dynamics in a trapped-ion system driven by a laser, additional series of collapses and revivals of the vibrational state of the ion can be generated.

Evaluation of laser-driven ion energies for fusion fast-ignition research

NASA Astrophysics Data System (ADS)

Tosaki, S.; Yogo, A.; Koga, K.; Okamoto, K.; Shokita, S.; Morace, A.; Arikawa, Y.; Fujioka, S.; Nakai, M.; Shiraga, H.; Azechi, H.; Nishimura, H.

2017-10-01

We investigate laser-driven ion acceleration using kJ-class picosecond (ps) laser pulses as a fundamental study for ion-assisted fusion fast ignition, using a newly developed Thomson-parabola ion spectrometer (TPIS). The TPIS has a space- and weight-saving design, considering its use in an laser-irradiation chamber in which 12 beams of fuel implosion laser are incident, and, at the same time, demonstrates sufficient performance with its detectable range and resolution of the ion energy required for fast-ignition research. As a fundamental study on laser-ion acceleration using a ps pulse laser, we show proton acceleration up to 40 MeV at 1 × 10^{19} W cm^{-2}. The energy conversion efficiency from the incident laser into protons higher than 6 MeV is 4.6%, which encourages the realization of fusion fast ignition by laser-driven ions.

Quasi-monoenergetic ion beam acceleration by laser-driven shock and solitary waves in near-critical plasmas

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

Zhang, W. L.; Qiao, B., E-mail: bqiao@pku.edu.cn; Huang, T. W.

2016-07-15

Ion acceleration in near-critical plasmas driven by intense laser pulses is investigated theoretically and numerically. A theoretical model has been given for clarification of the ion acceleration dynamics in relation to different laser and target parameters. Two distinct regimes have been identified, where ions are accelerated by, respectively, the laser-induced shock wave in the weakly driven regime (comparatively low laser intensity) and the nonlinear solitary wave in the strongly driven regime (comparatively high laser intensity). Two-dimensional particle-in-cell simulations show that quasi-monoenergetic proton beams with a peak energy of 94.6 MeV and an energy spread 15.8% are obtained by intense laser pulsesmore » at intensity I{sub 0} = 3 × 10{sup 20 }W/cm{sup 2} and pulse duration τ = 0.5 ps in the strongly driven regime, which is more advantageous than that got in the weakly driven regime. In addition, 233 MeV proton beams with narrow spread can be produced by extending τ to 1.0 ps in the strongly driven regime.« less

catena-Poly[[(benzil bis{[(pyridin-2-yl)methylidene]hydrazone}-κ4 N,N′,N′′,N′′′)mercury(II)]-μ-chlorido-[dichloridomercury(II)]-μ-chlorido

PubMed Central

Akkurt, Mehmet; Khandar, Ali Akbar; Tahir, Muhammad Nawaz; Hosseini-Yazdi, Seyed Abolfazl; Mahmoudi, Ghodrat

2012-01-01

In the title coordination polymer, [Hg2Cl4(C26H20N6)]n, one HgII ion is coordinated by four N atoms from the benzylbis((pyridin-2-yl)methyl­idenehydrazone) ligand and two Cl− ions in a very distorted cis-HgCl2N4 octa­hedral geometry. The other HgII ion is coordinated in a distorted tetra­hedral geometry by four Cl− ions. Bridging chloride ions link the HgII ions into a chain propagating in [010]: the Hg—Cl bridging bonds are significantly longer than the terminal bonds. The dihedral angle between the central benzene rings of the ligand is 83.3 (2)°. The packing is consolidated by weak C—H⋯Cl hydrogen bonds and C—H⋯π inter­actions. PMID:22807743

Complexation Enhancement Drives Water-to-Oil Ion Transport: A Simulation Study

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

Qiao, Baofu; Ferru, Geoffroy; Ellis, Ross J.

We address the structures and energetics of ion solvation in aqueous and organic solutions to understand liquid-liquid ion transport. Atomistic molecular dynamics (MD) simulations with polarizable force field are performed to study the coordination transformations driving lanthanide (Ln(III)) and nitrate ion transport between aqueous and an alkylamide-oil solution. An enhancement of the coordination behavior in the organic phase is achieved in contrast with the aqueous solution. In particular, the coordination number of Ce3+ increases from 8.9 in the aqueous to 9.9 in the organic solutions (from 8 in the aqueous to 8.8 in the organic systems for Yb3+). Moreover, themore » local coordination environ ment changes dramatically. Potential of mean force calculations show that the Ln(III)-ligand coordination interaction strengths follow the order of Ln(III-)nitrate> Ln(III)-water>Ln(III)-DMDBTDMA. They increase 2-fold in the lipophilic environment in comparison to the aqueous phase, and we attribute this to the shedding of the outer solvation shell. Our findings highlight the importance of outer sphere interactions on the competitive solvation energetics that cause ions to migrate between immiscible phases; an essential ingredient for advancing important applications such as rare earth metal separations. Some open questions in simulating the coordination behavior of heavy metals are also addressed.« less

Suppression of energetic particle driven instabilities with HHFW heating

DOE PAGES

Fredrickson, E. D.; Taylor, G.; Bertelli, N.; ...

2015-01-01

In plasmas in the National Spherical Torus Experiment (NSTX) [Ono et al., Nucl. Fusion 40 (2000) 557] heated with neutral beams, the beam ions typically excite Energetic Particle Modes (EPMs or fishbones), and Toroidal, Global or Compressional Alfvén Eigenmodes (TAE, GAE, CAE). These modes can redistribute the energetic beam ions, altering the beam driven current profile and the plasma heating profile, or they may affect electron thermal transport or cause losses of the beam ions. In this paper we present experimental results where these instabilities, driven by the super-thermal beam ions, are suppressed with the application of High Harmonic Fastmore » Wave heating.« less

Helium-3 and helium-4 acceleration by high power laser pulses for hadron therapy

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

Bulanov, S. S.; Esarey, E.; Schroeder, C. B.

The laser driven acceleration of ions is considered a promising candidate for an ion source for hadron therapy of oncological diseases. Though proton and carbon ion sources are conventionally used for therapy, other light ions can also be utilized. Whereas carbon ions require 400 MeV per nucleon to reach the same penetration depth as 250 MeV protons, helium ions require only 250 MeV per nucleon, which is the lowest energy per nucleon among the light ions (heavier than protons). This fact along with the larger biological damage to cancer cells achieved by helium ions, than that by protons, makes thismore » species an interesting candidate for the laser driven ion source. Two mechanisms (magnetic vortex acceleration and hole-boring radiation pressure acceleration) of PW-class laser driven ion acceleration from liquid and gaseous helium targets are studied with the goal of producing 250 MeV per nucleon helium ion beams that meet the hadron therapy requirements. We show that He3 ions, having almost the same penetration depth as He4 with the same energy per nucleon, require less laser power to be accelerated to the required energy for the hadron therapy.« less

Helium-3 and helium-4 acceleration by high power laser pulses for hadron therapy

DOE PAGES

Bulanov, S. S.; Esarey, E.; Schroeder, C. B.; ...

2015-06-24

The laser driven acceleration of ions is considered a promising candidate for an ion source for hadron therapy of oncological diseases. Though proton and carbon ion sources are conventionally used for therapy, other light ions can also be utilized. Whereas carbon ions require 400 MeV per nucleon to reach the same penetration depth as 250 MeV protons, helium ions require only 250 MeV per nucleon, which is the lowest energy per nucleon among the light ions (heavier than protons). This fact along with the larger biological damage to cancer cells achieved by helium ions, than that by protons, makes thismore » species an interesting candidate for the laser driven ion source. Two mechanisms (magnetic vortex acceleration and hole-boring radiation pressure acceleration) of PW-class laser driven ion acceleration from liquid and gaseous helium targets are studied with the goal of producing 250 MeV per nucleon helium ion beams that meet the hadron therapy requirements. We show that He3 ions, having almost the same penetration depth as He4 with the same energy per nucleon, require less laser power to be accelerated to the required energy for the hadron therapy.« less

A mechanism for beam-driven excitation of ion cyclotron harmonic waves in the Tokamak Fusion Test Reactor

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

Dendy, R.O.; McClements, K.G.; Lashmore-Davies, C.N.

1994-10-01

A mechanism is proposed for the excitation of waves at harmonics of the injected ion cyclotron frequencies in neutral beam-heated discharges in the Tokamak Fusion Test Reactor (TFTR) [[ital Proceedings] [ital of] [ital the] 17[ital th] [ital European] [ital Conference] [ital on] [ital Controlled] [ital Fusion] [ital and] [ital Plasma] [ital Heating] (European Physical Society, Petit-Lancy, Switzerland, 1990), p. 1540]. Such waves are observed to originate from the outer midplane edge of the plasma. It is shown that ion cyclotron harmonic waves can be destabilized by a low concentration of sub-Alfvenic deuterium or tritium beam ions, provided these ions havemore » a narrow distribution of speeds parallel to the magnetic field. Such a distribution is likely to occur in the edge plasma, close to the point of beam injection. The predicted instability gives rise to wave emission at propagation angles lying almost perpendicular to the field. In contrast to the magnetoacoustic cyclotron instability proposed as an excitation mechanism for fusion-product-driven ion cyclotron emission in the Joint European Torus (JET) [Phys. Plasmas [bold 1], 1918 (1994)], the instability proposed here does not involve resonant fast Alfven and ion Bernstein waves, and can be driven by sub-Alfvenic energetic ions. It is concluded that the observed emission from TFTR can be driven by beam ions.« less

Geometric and energetic considerations of surface fluctuations during ion transfer across the water-immiscible organic liquid interface

NASA Astrophysics Data System (ADS)

Karnes, John J.; Benjamin, Ilan

2016-07-01

Molecular dynamics simulations and umbrella sampling free energy calculations are used to examine the thermodynamics, energetics, and structural fluctuations that accompany the transfer of a small hydrophilic ion (Cl-) across the water/nitrobenzene interface. By examining several constrained interface structures, we isolate the energetic costs of interfacial deformation and co-transfer of hydration waters during the ion transfer. The process is monitored using both energy-based solvation coordinates and a geometric coordinate recently introduced by Morita and co-workers to describe surface fluctuations. Our simulations show that these coordinates provide a complimentary description of the water surface fluctuations during the transfer and are necessary for elucidating the mechanism of the ion transfer.

Headgroup interactions and ion flotation efficiency in mixtures of a chelating surfactant, different foaming agents, and divalent metal ions.

PubMed

Svanedal, Ida; Boija, Susanne; Norgren, Magnus; Edlund, Håkan

2014-06-10

The correlation between interaction parameters and ion flotation efficiency in mixtures of chelating surfactant metal complexes and different foaming agents was investigated. We have recently shown that chelating surfactant 2-dodecyldiethylenetriaminepentaacetic acid (4-C12-DTPA) forms strong coordination complexes with divalent metal ions, and this can be utilized in ion flotation. Interaction parameters for mixed micelles and mixed monolayer formation for Mg(2+) and Ni(2+) complexes with the chelating surfactant 4-C12-DTPA and different foaming agents were calculated by Rubingh's regular solution theory. Parameters for the calculations were extracted from surface tension measurements and NMR diffusometry. The effects of metal ion coordination on the interactions between 4-C12-DTPA and the foaming agents could be linked to a previously established difference in coordination chemistry between the examined metal ions. As can be expected from mixtures of amphoteric surfactants, the interactions were strongly pH-dependent. Strong correlation was found between interaction parameter β(σ) for mixed monolayer formation and the phase-transfer efficiency of Ni(2+) complexes with 4-C12-DTPA during flotation in a customized flotation cell. In a mixture of Cu(2+) and Zn(2+), the significant difference in conditional stability constants (log K) between the metal complexes was utilized to selectively recover the metal complex with the highest log K (Cu(2+)) by ion flotation. Flotation experiments in an excess concentration of metal ions confirmed the coordination of more than one metal ion to the headgroup of 4-C12-DTPA.

Synthesis and Characterization of Templated Ion Exchange Resins for the Selective Complexion of Actinide Ions

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

Murrray, George M.; Uy, O. Manuel

The purpose of this research is to develop polymeric extractants for the selective complexation of uranyl ions (and subsequently other actinyl and actinide ions) from aqueous solutions. Selectivity for a specific actinide ion is obtained by providing the polymers with cavities lined with complexing ligands so arranged as to match the charge, coordination number, coordination geometry, and size of the actinide ion. These cavity-containing polymers are produced by using a specific actinide ion (or surrogate) as a template around which monomeric complexing ligands are polymerized. The polymers provide useful sequestering agents for removing actinide ions from wastes and will formmore » the basis for a variety of analytical techniques for actinide determination.« less

On the Role of Ionospheric Ions in Sawtooth Events

NASA Astrophysics Data System (ADS)

Lund, E. J.; Nowrouzi, N.; Kistler, L. M.; Cai, X.; Frey, H. U.

2018-01-01

Simulations have suggested that feedback of heavy ions originating in the ionosphere is an important mechanism for driving sawtooth injections. However, this feedback may only be necessary for events driven by coronal mass ejections (CMEs), whereas in events driven by streaming interaction regions (SIRs), solar wind variability may suffice to drive these injections. Here we present case studies of two sawtooth events for which in situ data are available in both the magnetotail (Cluster) and the nightside auroral region (FAST), as well as global auroral images (IMAGE). One event, on 1 October 2001, was driven by a CME; the other, on 24 October 2002, was driven by an SIR. The available data do not support the hypothesis that heavy ion feedback is necessary to drive either event. This result is consistent with simulations of the SIR-driven event but disagrees with simulation results for a different CME-driven event. We also find that in an overwhelming majority of the sawtooth injections for which Cluster tail data are available, the O+ observed in the tail comes from the cusp rather than the nightside auroral region, which further casts doubt on the hypothesis that ionospheric heavy ion feedback is the cause of sawtooth injections.

Specific binding of trivalent metal ions to λ-carrageenan.

PubMed

Cao, Yiping; Li, Shugang; Fang, Yapeng; Nishinari, Katsuyoshi; Phillips, Glyn O; Lerbret, Adrien; Assifaoui, Ali

2018-04-01

Carrageenans are a family of sulphated cell wall polysaccharides extracted from seaweeds and are widely used in different industrial sectors. Relative to κ-carrageenan (κ-car) and ι-carrageenan (ι-car), the ionic binding behavior of λ-carrageenan (λ-car) is far less studied. In this work, the interaction and binding behavior between λ-car and metal ions of different valency (Na + , K + , Mg 2+ , Ca 2+ , Fe 2+ , Fe 3+ , Al 3+ , Cr 3+ ) have been investigated. In contrast to the non-specific interaction of the monovalent and divalent cations, specific binding has been identified between λ-car and Fe 3+ /Al 3+ . The specific binding could lead to either precipitation or gelation of λ-car, depending on the way of introducing Fe 3+ /Al 3+ ions. Fe 3+ and Al 3+ exhibit the same binding stoichiometry of [M 3+ ]/[repeating unit] = 1.0, with the former having a relatively larger binding constant. Cr 3+ , though having very similar physical properties with Fe 3+ /Al 3+ , is incapable of binding specifically to Cr 3+ . The phenomena could not be interpreted in terms of counterion condensation, and are rather attributable to a mechanism in which hexa-coordination of Fe 3+ /Al 3+ and entropy-driven cation dehydration play crucial roles in driving the binding of the trivalent metal ions to λ-car. Copyright © 2017 Elsevier B.V. All rights reserved.

Carbonate-sensitive phytotransferrin controls high-affinity iron uptake in diatoms

NASA Astrophysics Data System (ADS)

McQuaid, Jeffrey B.; Kustka, Adam B.; Oborník, Miroslav; Horák, Aleš; McCrow, John P.; Karas, Bogumil J.; Zheng, Hong; Kindeberg, Theodor; Andersson, Andreas J.; Barbeau, Katherine A.; Allen, Andrew E.

2018-03-01

In vast areas of the ocean, the scarcity of iron controls the growth and productivity of phytoplankton. Although most dissolved iron in the marine environment is complexed with organic molecules, picomolar amounts of labile inorganic iron species (labile iron) are maintained within the euphotic zone and serve as an important source of iron for eukaryotic phytoplankton and particularly for diatoms. Genome-enabled studies of labile iron utilization by diatoms have previously revealed novel iron-responsive transcripts, including the ferric iron-concentrating protein ISIP2A, but the mechanism behind the acquisition of picomolar labile iron remains unknown. Here we show that ISIP2A is a phytotransferrin that independently and convergently evolved carbonate ion-coordinated ferric iron binding. Deletion of ISIP2A disrupts high-affinity iron uptake in the diatom Phaeodactylum tricornutum, and uptake is restored by complementation with human transferrin. ISIP2A is internalized by endocytosis, and manipulation of the seawater carbonic acid system reveals a second-order dependence on the concentrations of labile iron and carbonate ions. In P. tricornutum, the synergistic interaction of labile iron and carbonate ions occurs at environmentally relevant concentrations, revealing that carbonate availability co-limits iron uptake. Phytotransferrin sequences have a broad taxonomic distribution and are abundant in marine environmental genomic datasets, suggesting that acidification-driven declines in the concentration of seawater carbonate ions will have a negative effect on this globally important eukaryotic iron acquisition mechanism.

Laser acceleration of quasi-monoenergetic MeV ion beams.

PubMed

Hegelich, B M; Albright, B J; Cobble, J; Flippo, K; Letzring, S; Paffett, M; Ruhl, H; Schreiber, J; Schulze, R K; Fernández, J C

2006-01-26

Acceleration of particles by intense laser-plasma interactions represents a rapidly evolving field of interest, as highlighted by the recent demonstration of laser-driven relativistic beams of monoenergetic electrons. Ultrahigh-intensity lasers can produce accelerating fields of 10 TV m(-1) (1 TV = 10(12) V), surpassing those in conventional accelerators by six orders of magnitude. Laser-driven ions with energies of several MeV per nucleon have also been produced. Such ion beams exhibit unprecedented characteristics--short pulse lengths, high currents and low transverse emittance--but their exponential energy spectra have almost 100% energy spread. This large energy spread, which is a consequence of the experimental conditions used to date, remains the biggest impediment to the wider use of this technology. Here we report the production of quasi-monoenergetic laser-driven C5+ ions with a vastly reduced energy spread of 17%. The ions have a mean energy of 3 MeV per nucleon (full-width at half-maximum approximately 0.5 MeV per nucleon) and a longitudinal emittance of less than 2 x 10(-6) eV s for pulse durations shorter than 1 ps. Such laser-driven, high-current, quasi-monoenergetic ion sources may enable significant advances in the development of compact MeV ion accelerators, new diagnostics, medical physics, inertial confinement fusion and fast ignition.

Target-induced formation of gold amalgamation on DNA-based sensing platform for electrochemical monitoring of mercury ion coupling with cycling signal amplification strategy.

PubMed

Chen, Jinfeng; Tang, Juan; Zhou, Jun; Zhang, Lan; Chen, Guonan; Tang, Dianping

2014-01-31

Heavy metal ion pollution poses severe risks in human health and environmental pollutant, because of the likelihood of bioaccumulation and toxicity. Driven by the requirement to monitor trace-level mercury ion (Hg(2+)), herein we construct a new DNA-based sensor for sensitive electrochemical monitoring of Hg(2+) by coupling target-induced formation of gold amalgamation on DNA-based sensing platform with gold amalgamation-catalyzed cycling signal amplification strategy. The sensor was simply prepared by covalent conjugation of aminated poly-T(25) oligonucleotide onto the glassy carbon electrode by typical carbodiimide coupling. Upon introduction of target analyte, Hg(2+) ion was intercalated into the DNA polyion complex membrane based on T-Hg(2+)-T coordination chemistry. The chelated Hg(2+) ion could induce the formation of gold amalgamation, which could catalyze the p-nitrophenol with the aid of NaBH4 and Ru(NH3)6(3+) for cycling signal amplification. Experimental results indicated that the electronic signal of our system increased with the increasing Hg(2+) level in the sample, and has a detection limit of 0.02nM with a dynamic range of up to 1000nM Hg(2+). The strategy afforded exquisite selectivity for Hg(2+) against other environmentally related metal ions. In addition, the methodology was evaluated for the analysis of Hg(2+) in spiked tap-water samples, and the recovery was 87.9-113.8%. Copyright © 2013 Elsevier B.V. All rights reserved.

Generation of quasi-monoenergetic heavy ion beams via staged shock wave acceleration driven by intense laser pulses in near-critical plasmas

NASA Astrophysics Data System (ADS)

Zhang, W. L.; Qiao, B.; Shen, X. F.; You, W. Y.; Huang, T. W.; Yan, X. Q.; Wu, S. Z.; Zhou, C. T.; He, X. T.

2016-09-01

Laser-driven ion acceleration potentially offers a compact, cost-effective alternative to conventional accelerators for scientific, technological, and health-care applications. A novel scheme for heavy ion acceleration in near-critical plasmas via staged shock waves driven by intense laser pulses is proposed, where, in front of the heavy ion target, a light ion layer is used for launching a high-speed electrostatic shock wave. This shock is enhanced at the interface before it is transmitted into the heavy ion plasmas. Monoenergetic heavy ion beam with much higher energy can be generated by the transmitted shock, comparing to the shock wave acceleration in pure heavy ion target. Two-dimensional particle-in-cell simulations show that quasi-monoenergetic {{{C}}}6+ ion beams with peak energy 168 MeV and considerable particle number 2.1 × {10}11 are obtained by laser pulses at intensity of 1.66 × {10}20 {{W}} {{cm}}-2 in such staged shock wave acceleration scheme. Similarly a high-quality {{Al}}10+ ion beam with a well-defined peak with energy 250 MeV and spread δ E/{E}0=30 % can also be obtained in this scheme.

Investigation of ion kinetic effects in direct-drive exploding-pusher implosions at the NIF

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

Rosenberg, M. J., E-mail: mrosenbe@mit.edu; Zylstra, A. B.; Séguin, F. H.

Measurements of yield, ion temperature, areal density (ρR), shell convergence, and bang time have been obtained in shock-driven, D{sub 2} and D{sup 3}He gas-filled “exploding-pusher” inertial confinement fusion (ICF) implosions at the National Ignition Facility to assess the impact of ion kinetic effects. These measurements probed the shock convergence phase of ICF implosions, a critical stage in hot-spot ignition experiments. The data complement previous studies of kinetic effects in shock-driven implosions. Ion temperature and fuel ρR inferred from fusion-product spectroscopy are used to estimate the ion-ion mean free path in the gas. A trend of decreasing yields relative to themore » predictions of 2D DRACO hydrodynamics simulations with increasing Knudsen number (the ratio of ion-ion mean free path to minimum shell radius) suggests that ion kinetic effects are increasingly impacting the hot fuel region, in general agreement with previous results. The long mean free path conditions giving rise to ion kinetic effects in the gas are often prevalent during the shock phase of both exploding pushers and ablatively driven implosions, including ignition-relevant implosions.« less

Superposed epoch analysis of ion temperatures during CME- and CIR/HSS-driven storms

NASA Astrophysics Data System (ADS)

Keesee, A. M.; Scime, E. E.

2012-12-01

The NASA Two Wide-angle Imaging Neutral atom Spectrometers (TWINS) Mission provides a global view of the magnetosphere with near-continuous coverage. Utilizing a novel technique to calculate ion temperatures from the TWINS energetic neutral atom (ENA) measurements, we generate ion temperature maps of the magnetosphere. These maps can be used to study ion temperature evolution during geomagnetic storms. A superposed epoch analysis of the ion temperature evolution during 48 storms will be presented. Zaniewski et al. [2006] performed a superposed epoch analysis of ion temperatures by storm interval using data from the MENA instrument on the IMAGE mission, demonstrating significant dayside ion heating during the main phase. The TWINS measurements provide more continuous coverage and improved spatial and temporal resolution. Denton and Borovsky [2008] noted differences in ion temperature evolution at geosynchronous orbit between coronal mass ejection (CME)- and corotating interaction region (CIR)/high speed stream (HSS)- driven storms. Using our global ion temperature maps, we have found consistent results for select individual storms [Keesee et al., 2012]. We will present superposed epoch analyses for the subgroups of CME- and CIR/HSS-driven storms to compare global ion temperature evolution during the two types of storms.

Poly[diaqua­tris­(μ4-1,3-phenyl­enediacetato)­dineodymium(III)

PubMed Central

Gao, Zhu-Qing; Lv, Dong-Yu; Li, Hong-Ji; Gu, Jin-Zhong

2011-01-01

In the title coordination polymer, [Nd2(C10H8O4)3(H2O)2]n, each of the two NdIII ions is nine-coordinated by eight O atoms from six different 2,2′-(m-phenyl­ene)diacetate (pda) bivalent anions and by one O atom from a water mol­ecule, forming a distorted tricapped trigonal–prismatic coordination geometry. Eight NdIII ions and 12 pda ligands form a large [Nd8(pda)12] ring, and four NdIII ions and six pda ligands form a small [Nd4(pda)6] ring. These rings are further connected by the coordination inter­actions of pda ligands and NdIII, generating a three-dimensional supra­molecular framework. PMID:21522305

Fast ion beta limit measurements by collimated neutron detection in MST plasmas

NASA Astrophysics Data System (ADS)

Capecchi, William; Anderson, Jay; Bonofiglo, Phillip; Kim, Jungha; Sears, Stephanie

2015-11-01

Fast ion orbits in the reversed field pinch (RFP) are well ordered and classically confined despite magnetic field stochasticity generated by multiple tearing modes. Classical TRANSP modeling of a 1MW tangentially injected hydrogen neutral beam in MST deuterium plasmas predicts a core-localized fast ion density that can be up to 25% of the electron density and a fast ion beta of many times the local thermal beta. However, neutral particle analysis of an NBI-driven mode (presumably driven by a fast ion pressure gradient) shows mode-induced transport of core-localized fast ions and a saturated fast ion density. The TRANSP modeling is presumed valid until the onset of the beam-driven mode and gives an initial estimate of the volume-averaged fast ion beta of 1-2% (local core value up to 10%). A collimated neutron detector for fusion product profile measurements will be used to determine the spatial distribution of fast ions, allowing for a first measurement of the critical fast-ion pressure gradient required for mode destabilization. Testing/calibration data and initial fast-ion profiles will be presented. Characterization of both the local and global fast ion beta will be done for deuterium beam injection into deuterium plasmas for comparison to TRANSP predictions. Work supported by US DOE.

Syntheses and structural characterization of iron(II) and copper(II) coordination compounds with the neutral flexible bidentate N-donor ligands

NASA Astrophysics Data System (ADS)

Beheshti, Azizolla; Lalegani, Arash; Bruno, Giuseppe; Rudbari, Hadi Amiri

2014-08-01

Two new coordination compounds [Fe(bib)2(N3)2]n(1) and [Cu2(bpp)2(N3)4] (2) with azide and flexible ligands 1,4-bis(imidazolyl)butane (bib) and 1,3-bis(3,5-dimethylpyrazolyl)propane (bpp) were prepared and structurally characterized. In the 2D network structure of 1, the iron(II) ion lies on an inversion center and exhibits an FeN6 octahedral arrangement while in the dinuclear structure of 2, the copper(II) ion adopts an FeN5 distorted square pyramid geometry. In the complex 1, each μ2-bib acts as bridging ligand connecting two adjacent iron(II) ions while in the complex 2, the bpp ligand is coordinated to copper(II) ion in a cyclic-bidentate fashion forming an eight-membered metallocyclic ring. Coordination compounds 1 and 2 have been characterized by infrared spectroscopy, elemental analyses and single-crystal X-ray diffraction. Thermal analysis of polymer 1 was also studied.

Broadband white light emission from Ce:AlN ceramics: High thermal conductivity down-converters for LED and laser-driven solid state lighting

NASA Astrophysics Data System (ADS)

Wieg, A. T.; Penilla, E. H.; Hardin, C. L.; Kodera, Y.; Garay, J. E.

2016-12-01

We introduce high thermal conductivity aluminum nitride (AlN) as a transparent ceramic host for Ce3+, a well-known active ion dopant. We show that the Ce:AlN ceramics have overlapping photoluminescent (PL) emission peaks that cover almost the entire visible range resulting in a white appearance under 375 nm excitation without the need for color mixing. The PL is due to a combination of intrinsic AlN defect complexes and Ce3+ electronic transitions. Importantly, the peak intensities can be tuned by varying the Ce concentration and processing parameters, causing different shades of white light without the need for multiple phosphors or light sources. The Commission Internationale de l'Eclairage coordinates calculated from the measured spectra confirm white light emission. In addition, we demonstrate the viability of laser driven white light emission by coupling the Ce:AlN to a readily available frequency tripled Nd-YAG laser emitting at 355 nm. The high thermal conductivity of these ceramic down-converters holds significant promise for producing higher power white light sources than those available today.

Reduced Graphene Oxide-Immobilized Tris(bipyridine)ruthenium(II) Complex for Efficient Visible-Light-Driven Reductive Dehalogenation Reaction.

PubMed

Li, Xiaoyan; Hao, Zhongkai; Zhang, Fang; Li, Hexing

2016-05-18

A sodium benzenesulfonate (PhSO3Na)-functionalized reduced graphene oxide was synthesized via a two-step aryl diazonium coupling and subsequent NaCl ion-exchange procedure, which was used as a support to immobilize tris(bipyridine)ruthenium(II) complex (Ru(bpy)3Cl2) by coordination reaction. This elaborated Ru(bpy)3-rGO catalyst exhibited excellent catalytic efficiency in visible-light-driven reductive dehalogenation reactions under mild conditions, even for ary chloride. Meanwhile, it showed the comparable reactivity with the corresponding homogeneous Ru(bpy)3Cl2 catalyst. This high catalytic performance could be attributed to the unique two-dimensional sheet-like structure of Ru(bpy)3-rGO, which efficiently diminished diffusion resistance of the reactants. Meanwhile, the nonconjugated PhSO3Na-linkage between Ru(II) complex and the support and the very low electrical conductivity of the catalyst inhibited energy/electron transfer from Ru(II) complex to rGO support, resulting in the decreased support-induced quenching effect. Furthermore, it could be easily recycled at least five times without significant loss of catalytic reactivity.

Nonlinear response and bistability of driven ion acoustic waves

NASA Astrophysics Data System (ADS)

Akbari-Moghanjoughi, M.

2017-08-01

The hydrodynamic model is used to obtain a generalized pseudoforce equation through which the nonlinear response of periodically driven ion acoustic waves is studied in an electron-ion plasma with isothermal and adiabatic ion fluids. The pseudotime series, corresponding to different driving frequencies, indicates that nonlinearity effects appear more strongly for smaller frequency values. The existence of extra harmonic resonances in the nonlinear amplitude spectrum is a clear indication of the interaction of an external force with harmonic components of the nonlinear ion acoustic waves. It is shown that many plasma parameters significantly and differently affect the nonlinear resonance spectrum of ion acoustic excitations. A heuristic but accurate model for the foldover effect is used which quite satisfactorily predicts the bistability of driven plasma oscillations. It is remarked that the characteristic resonance peak of isothermal ion plasma oscillations appears at lower frequencies but is stronger compared to that of adiabatic ions. Comparison of the exact numerical results for fully nonlinear and approximate (weakly nonlinear) models indicates that a weakly nonlinear model exaggerates the hysteresis and jump phenomenon for higher values of the external force amplitude.

Laser-ablation-based ion source characterization and manipulation for laser-driven ion acceleration

NASA Astrophysics Data System (ADS)

Sommer, P.; Metzkes-Ng, J.; Brack, F.-E.; Cowan, T. E.; Kraft, S. D.; Obst, L.; Rehwald, M.; Schlenvoigt, H.-P.; Schramm, U.; Zeil, K.

2018-05-01

For laser-driven ion acceleration from thin foils (∼10 μm–100 nm) in the target normal sheath acceleration regime, the hydro-carbon contaminant layer at the target surface generally serves as the ion source and hence determines the accelerated ion species, i.e. mainly protons, carbon and oxygen ions. The specific characteristics of the source layer—thickness and relevant lateral extent—as well as its manipulation have both been investigated since the first experiments on laser-driven ion acceleration using a variety of techniques from direct source imaging to knife-edge or mesh imaging. In this publication, we present an experimental study in which laser ablation in two fluence regimes (low: F ∼ 0.6 J cm‑2, high: F ∼ 4 J cm‑2) was applied to characterize and manipulate the hydro-carbon source layer. The high-fluence ablation in combination with a timed laser pulse for particle acceleration allowed for an estimation of the relevant source layer thickness for proton acceleration. Moreover, from these data and independently from the low-fluence regime, the lateral extent of the ion source layer became accessible.

Stoichiometric Control of Multiple Different Tectons in Coordination-Driven Self-assembly

PubMed Central

Lee, Junseong; Ghosh, Koushik; Stang, Peter J.

2009-01-01

We present a general strategy for the synthesis of stable, multi-component fused polygon complexes where coordination-driven self-assembly allows for single supramolecular species can be formed from multi-component self-assembly and the shape of the obtained polygons can be controlled by simply changing the ratio of individual components. The compounds are characterized by Multinuclear NMR, ESI Mass spectrometry. PMID:19663439

Metal ion interaction with phosphorylated tyrosine analogue monolayers on gold.

PubMed

Petoral, Rodrigo M; Björefors, Fredrik; Uvdal, Kajsa

2006-11-23

Phosphorylated tyrosine analogue molecules (pTyr-PT) were assembled onto gold substrates, and the resulting monolayers were used for metal ion interaction studies. The monolayers were characterized by X-ray photoelectron spectroscopy (XPS), infrared reflection-absorption spectroscopy (IRAS), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS), both prior to and after exposure to metal ions. XPS verified the elemental composition of the molecular adsorbate and the presence of metal ions coordinated to the phosphate groups. Both the angle-dependent XPS and IRAS results were consistent with the change in the structural orientation of the pTyr-PT monolayer upon exposure to metal ions. The differential capacitance of the monolayers upon coordination of the metal ions was evaluated using EIS. These metal ions were found to significantly change the capacitance of the pTyr-PT monolayers in contrast to the nonphosphorylated tyrosine analogue (TPT). CV results showed reduced electrochemical blocking capabilities of the phosphorylated analogue monolayer when exposed to metal ions, supporting the change in the structure of the monolayer observed by XPS and IRAS. The largest change in the structure and interfacial capacitance was observed for aluminum ions, compared to calcium, magnesium, and chromium ions. This type of monolayer shows an excellent capability to coordinate metal ions and has a high potential for use as sensing layers in biochip applications to monitor the presence of metal ions.

Synthesis, structure, and luminescence property of a series of Ag–Ln coordination polymers with the N-heterocyclic carboxylato ligand

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

Jin, Jing, E-mail: jinjing_crystal@126.com; Chen, Chong; Gao, Yan

Six Ln–Ag coordination polymers {[LnAg_2(IN)_4(H_2O)_5]·NO_3·2H_2O}{sub n} (Ln=Ho (1) and Tb (2), HIN=isonicotinic acid), {[PrAg_2(IN)_4(H_2O)_2]·NO_3·H_2O}{sub n} (3), [LnAg(pdc){sub 2}]{sub n} (Ln=Eu(4) and Pr (5), H{sub 2}pdc=3,4-pyridine-dicarboxylic acid) and [NdAg(bidc){sub 2}(H{sub 2}O){sub 4}]{sub n} (6) (H{sub 2}bidc=benzimidazole-5,6-dicarboxylic acid) have been hydrothermally synthesized and characterized by single crystal X-ray diffraction, elemental analysis, IR, UV–vis-NIR absorption spectra, fluorescence spectra and thermogravimetric analysis. Structural analyses reveal that the six polymers exhibit 0D (polymer (1)), 1D (polymer (2)), 2D (polymers (3) and (5)) and 3D (polymers (4) and (6)) infinite structures, respectively. Polymers (1)–(6) exhibit the Ln(III) characteristic emission in the near-infrared (NIR) region or inmore » the visible region. Especially, the NIR emission bands of polymers 1, 5 and 6 evidently present shift or splitting due to formation of the Ln–Ag coordination polymers. This can be attributed to the tune of inner levels in Ln–Ag system caused by the interact and influence between the 4d orbital of the Ag(I) ion and the 4f orbital of the Ln(III) ion, which can be confirmed by the UV–vis-NIR absorption spectra of the polymers. In addition, the distortion of coordination geometry as well as difference of the coordination number around the Ag(I) ion affect the structure framework. - Graphical abstract: Six Ag–Ln coordination polymers have been hydrothermally synthesized and characterized. The photoluminescence properties were studied. The distortion of coordination geometry of Ag(I) ion affect structure framework. Introduction of Ag(I) cause wonderful changes to the NIR emission of Ln(III) ions. - Highlights: • Six Ln–Ag polymers have been synthesized and characterized. • The distortion of coordination geometry of Ag(I) ion affect structure framework. • Introduction of Ag(I) cause wonderful changes to the NIR emission of Ln(III) ions.« less

N-(sulfoethyl) iminodiacetic acid-based lanthanide coordination polymers: Synthesis, magnetism and quantum Monte Carlo studies

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

Zhuang Guilin, E-mail: glzhuang@zjut.edu.cn; Chen Wulin; Zheng Jun

2012-08-15

A series of lanthanide coordination polymers have been obtained through the hydrothermal reaction of N-(sulfoethyl) iminodiacetic acid (H{sub 3}SIDA) and Ln(NO{sub 3}){sub 3} (Ln=La, 1; Pr, 2; Nd, 3; Gd, 4). Crystal structure analysis exhibits that lanthanide ions affect the coordination number, bond length and dimension of compounds 1-4, which reveal that their structure diversity can be attributed to the effect of lanthanide contraction. Furthermore, the combination of magnetic measure with quantum Monte Carlo(QMC) studies exhibits that the coupling parameters between two adjacent Gd{sup 3+} ions for anti-anti and syn-anti carboxylate bridges are -1.0 Multiplication-Sign 10{sup -3} and -5.0 Multiplication-Signmore » 10{sup -3} cm{sup -1}, respectively, which reveals weak antiferromagnetic interaction in 4. - Graphical abstract: Four lanthanide coordination polymers with N-(sulfoethyl) iminodiacetic acid were obtained under hydrothermal condition and reveal the weak antiferromagnetic coupling between two Gd{sup 3+} ions by Quantum Monte Carlo studies. Highlights: Black-Right-Pointing-Pointer Four lanthanide coordination polymers of H{sub 3}SIDA ligand were obtained. Black-Right-Pointing-Pointer Lanthanide ions play an important role in their structural diversity. Black-Right-Pointing-Pointer Magnetic measure exhibits that compound 4 features antiferromagnetic property. Black-Right-Pointing-Pointer Quantum Monte Carlo studies reveal the coupling parameters of two Gd{sup 3+} ions.« less

On the Role of Ionospheric Ions in Sawtooth Events

NASA Astrophysics Data System (ADS)

Lund, E. J.; Nowrouzi, N.; Kistler, L. M.; Cai, X.; Frey, H. U.

2016-12-01

Global multifluid simulations have suggested that ions of ionospheric origin play a key role in driving sawtooth events, particularly events driven by coronal mass ejections (CMEs), through a feedback mechanism.1,2 The energy input from the first substorm causes ion outflow, which is claimed to drive the next substorm. We show that in situ data from Cluster in the tail during sawtooth events do not support this hypothesis. We show two detailed event studies, one driven by a CME and one driven by a streaming interaction region (SIR), as well as a statistical survey of all sawtooth events for which Cluster tail data are available. While examples exist of nightside outflow reaching the mid-tail ( 19 RE) region during CME-driven events, the overwhelming majority of both CME-driven and SIR-driven sawtooth injections have ionospheric ions in this region originating from the cusp, where the outflow is predominantly directly driven by the solar wind. The 19 RE region is critical because that is the region where near-Earth neutral line reconnection occurs. We conclude that while ionospheric outflow may contribute to sawtooth events, the injections are not the result of a feedback between the tail and the ionosphere. 1O. J. Brambles et al. (2011), Science 332, 1183, doi:10.1126/science.1202869.2O. J. Brambles et al. (2013), JGR 118, 6026, doi:10.1002/jgra.50522.

[2D correlation spectral study of a coordination polymer [Eu(PCPOA)3 (H2O)]n].

PubMed

Sun, Rui-qing; Zhang, Han-hui; Cao, Yan-ning; Chen, Yi-ping; Yang, Qi-yu; Wang, Zhi-yang

2007-05-01

A novel two dimensional coordination polymer [Eu(PCPOA)3 (H2O)], was synthesized under hydrothermal condition. Based on the determination of the structure, the 2D correlation FTIR spectra with the perturbation of magnetism and the 2D correlation fluorescence spectra with the perturbation of temperature were investigated. The energy bonds were calculated using CASTEP Program of Material studio. The Europium ions are nine-coordinated and the ligands adopted two different modes to connect the Eu3+ ions to 2D layer structure. The study of the 2D-FTIR reveals that the carboxylates coordinate with the center ions not only as monodentate, but also as bidentate chelate. The 2D fluorescence spectra indicates that the transition of (5)D0-->(7)F2 is influenced intensively by the perturbation of temperature.

One ligand in dual roles: self-assembly of a bis-rhomboidal-shaped, three-dimensional molecular wheel.

PubMed

Lu, Xiaocun; Li, Xiaopeng; Guo, Kai; Wang, Jing; Huang, Mingjun; Wang, Jin-Liang; Xie, Ting-Zheng; Moorefield, Charles N; Cheng, Stephen Z D; Wesdemiotis, Chrys; Newkome, George R

2014-10-06

A facile high yield, self-assembly process that leads to a terpyridine-based, three-dimensional, bis-rhomboidal-shaped, molecular wheel is reported. The desired coordination-driven supramolecular wheel involves eight structurally distorted tristerpyridine (tpy) ligands possessing a 60° angle between the adjacent tpy units and twelve Zn(2+) ions. The tpy ligand plays dual roles in the self-assembly process: two are staggered at 180° to create the internal hub, while six produce the external rim. The wheel can be readily generated by mixing the tpy ligand and Zn(2+) in a stoichiometric ratio of 2:3; full characterization is provided by ESI-MS, NMR spectroscopy, and TEM imaging. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Open Gate of the KV1.2 Channel: Quantum Calculations Show the Key Role of Hydration

PubMed Central

Kariev, Alisher M.; Njau, Philipa; Green, Michael E.

2014-01-01

The open gate of the Kv1.2 voltage-gated potassium channel can just hold a hydrated K+ ion. Quantum calculations starting from the x-ray coordinates of the channel confirm this, showing little change from the x-ray coordinates for the protein. Water molecules not in the x-ray coordinates, and the ion itself, are placed by the calculation. The water molecules, including their orientation and hydrogen bonding, with and without an ion, are critical for the path of the ion, from the solution to the gate. A sequence of steps is postulated in which the potential experienced by the ion in the pore is influenced by the position of the ion. The gate structure, with and without the ion, has been optimized. The charges on the atoms and bond lengths have been calculated using natural bond orbital calculations, giving K+ ∼0.77 charges, rather than 1.0. The PVPV hinge sequence has been mutated in silico to PVVV (P407V in the 2A79 numbering). The water structure around the ion becomes discontinuous, separated into two sections, above and below the ion. PVPV conservation closely relates to maintaining the water structure. Finally, these results have implications concerning gating. PMID:24507595

Ion temperature gradient mode driven solitons and shocks

NASA Astrophysics Data System (ADS)

Zakir, U.; Adnan, Muhammad; Haque, Q.; Qamar, Anisa; Mirza, Arshad M.

2016-04-01

Ion temperature gradient (ITG) driven solitons and shocks are studied in a plasma having gradients in the equilibrium number density and equilibrium ion temperature. In the linear regime, it is found that the ion temperature and the ratio of the gradient scale lengths, ηi=Ln/LT , affect both the real frequency and the growth rate of the ITG driven wave instability. In the nonlinear regime, for the first time we derive a Korteweg de Vries-type equation for the ITG mode, which admits solitary wave solution. It is found that the ITG mode supports only compressive solitons. Further, it is noticed that the soliton amplitude and width are sensitive to the parameter ηi=Ln/LT . Second, in the presence of dissipation in the system, we obtain a Burger type equation, which admits the shock wave solution. This work may be useful to understand the low frequency electrostatic modes in inhomogeneous electron-ion plasma having density and ion temperature gradients. For illustration, the model has been applied to tokamak plasma.

Guided post-acceleration of laser-driven ions by a miniature modular structure

PubMed Central

Kar, Satyabrata; Ahmed, Hamad; Prasad, Rajendra; Cerchez, Mirela; Brauckmann, Stephanie; Aurand, Bastian; Cantono, Giada; Hadjisolomou, Prokopis; Lewis, Ciaran L. S.; Macchi, Andrea; Nersisyan, Gagik; Robinson, Alexander P. L.; Schroer, Anna M.; Swantusch, Marco; Zepf, Matt; Willi, Oswald; Borghesi, Marco

2016-01-01

All-optical approaches to particle acceleration are currently attracting a significant research effort internationally. Although characterized by exceptional transverse and longitudinal emittance, laser-driven ion beams currently have limitations in terms of peak ion energy, bandwidth of the energy spectrum and beam divergence. Here we introduce the concept of a versatile, miniature linear accelerating module, which, by employing laser-excited electromagnetic pulses directed along a helical path surrounding the laser-accelerated ion beams, addresses these shortcomings simultaneously. In a proof-of-principle experiment on a university-scale system, we demonstrate post-acceleration of laser-driven protons from a flat foil at a rate of 0.5 GeV m−1, already beyond what can be sustained by conventional accelerator technologies, with dynamic beam collimation and energy selection. These results open up new opportunities for the development of extremely compact and cost-effective ion accelerators for both established and innovative applications. PMID:27089200

Synaptic Plasticity and NO-cGMP-PKG Signaling Coordinately Regulate ERK-Driven Gene Expression in the Lateral Amygdala and in the Auditory Thalamus Following Pavlovian Fear Conditioning

ERIC Educational Resources Information Center

Ota, Kristie T.; Monsey, Melissa S.; Wu, Melissa S.; Young, Grace J.; Schafe, Glenn E.

2010-01-01

We have recently hypothesized that NO-cGMP-PKG signaling in the lateral nucleus of the amygdala (LA) during auditory fear conditioning coordinately regulates ERK-driven transcriptional changes in both auditory thalamic (MGm/PIN) and LA neurons that serve to promote pre- and postsynaptic alterations at thalamo-LA synapses, respectively. In the…

Synergistic effects on enantioselectivity of zwitterionic chiral stationary phases for separations of chiral acids, bases, and amino acids by HPLC.

PubMed

Hoffmann, Christian V; Pell, Reinhard; Lämmerhofer, Michael; Lindner, Wolfgang

2008-11-15

In an attempt to overcome the limited applicability scope of earlier proposed Cinchona alkaloid-based chiral weak anion exchangers (WAX) and recently reported aminosulfonic acid-based chiral strong cation exchangers (SCX), which are conceptionally restricted to oppositely charged solutes, their individual chiral selector (SO) subunits have been fused in a combinatorial synthesis approach into single, now zwitterionic, chiral SO motifs. The corresponding zwitterionic ion-exchange-type chiral stationary phases (CSPs) in fact combined the applicability spectra of the parent chiral ion exchangers allowing for enantioseparations of chiral acids and amine-type solutes in liquid chromatography using polar organic mode with largely rivaling separation factors as compared to the parent WAX and SCX CSPs. Furthermore, the application spectrum could be remarkably expanded to various zwitterionic analytes such as alpha- and beta-amino acids and peptides. A set of structurally related yet different CSPs consisting of either a quinine or quinidine alkaloid moiety as anion-exchange subunit and various chiral or achiral amino acids as cation-exchange subunits enabled us to derive structure-enantioselectivity relationships, which clearly provided strong unequivocal evidence for synergistic effects of the two oppositely charged ion-exchange subunits being involved in molecular recognition of zwitterionic analytes by zwitterionic SOs driven by double ionic coordination.

Synthesis, crystal structures and Hirshfeld surface analyses of two new Salen type nickel/sodium heteronuclear complexes

NASA Astrophysics Data System (ADS)

Mahlooji, Niloofar; Behzad, Mahdi; Tarahhomi, Atekeh; Maroney, Michael; Rudbari, Hadi Amiri; Bruno, Giuseppe; Ghanbari, Bahram

2016-04-01

Two new heteronuclear Nickel(II)/Sodium(I) complexes of a side-off compartmental Schiff base ligand were synthesized and characterized by spectroscopic methods. Crystal structures of both of the complexes were also obtained. The Schiff base ligand was synthesized from the condensation of meso-1,2-diphenyl-1,2-ethylenediamine with 2-hydroxy-3-methoxybenzaldehyde. In both of the complexes the Ni(II) ion is coordinated to the inner N2O2 coordination sphere with square-planar geometry and the Na(I) ion is coordinated to the outer O2 O2‧ coordination sphere. In Complex (1) with general formula [Ni(L)Na(CH3OH)(ClO4)] the sodium ion is seven coordinated while in (2) with general formula [{Ni(L)Na(OH2)}2(μ-Ni(CN)4)] the sodium ion is six coordinated. Intermolecular interactions in two studied complexes were analyzed using 3D Hirshfeld surfaces and corresponding 2D fingerprint plots. This analysis showed that the H … H and C … H/H … C contacts for both structures (altogether 67.5% of total Hirshfeld surface area for (1) and 77.6% for (2)) and the O … H/H … O (24.2%) for (1) and the N … H/H … N (8.1%) contacts for (2) were the characteristic intermolecular contacts in the related crystal structures.

Coordination and Hydrolysis of Plutonium Ions in Aqueous Solution using Car-Parrinello Molecular Dynamics Free Energy Simulations

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

Odoh, Samuel O.; Bylaska, Eric J.; De Jong, Wibe A.

Car-Parrinello molecular dynamics (CPMD) simulations have been used to examine the hydration structures, coordination energetics and the first hydrolysis constants of Pu3+, Pu4+, PuO2+ and PuO22+ ions in aqueous solution at 300 K. The coordination numbers and structural properties of the first shell of these ions are in good agreement with available experimental estimates. The hexavalent PuO22+ species is coordinated to 5 aquo ligands while the pentavalent PuO2+ complex is coordinated to 4 aquo ligands. The Pu3+ and Pu4+ ions are both coordinated to 8 water molecules. The first hydrolysis constants obtained for Pu3+ and PuO22+ are 6.65 and 5.70more » respectively, all within 0.3 pH units of the experimental values (6.90 and 5.50 respectively). The hydrolysis constant of Pu4+, 0.17, disagrees with the value of -0.60 in the most recent update of the Nuclear Energy Agency Thermochemical Database (NEA-TDB) but supports recent experimental findings. The hydrolysis constant of PuO2+, 9.51, supports the experimental results of Bennett et al. (Radiochim. Act. 1992, 56, 15). A correlation between the pKa of the first hydrolysis reaction and the effective charge of the plutonium center was found.« less

A 1D ion species model for an RF driven negative ion source

NASA Astrophysics Data System (ADS)

Turner, I.; Holmes, A. J. T.

2017-08-01

A one-dimensional model for an RF driven negative ion source has been developed based on an inductive discharge. The RF source differs from traditional filament and arc ion sources because there are no primary electrons present, and is simply composed of an antenna region (driver) and a main plasma discharge region. However the model does still make use of the classical plasma transport equations for particle energy and flow, which have previously worked well for modelling DC driven sources. The model has been developed primarily to model the Small Negative Ion Facility (SNIF) ion source at CCFE, but may be easily adapted to model other RF sources. Currently the model considers the hydrogen ion species, and provides a detailed description of the plasma parameters along the source axis, i.e. plasma temperature, density and potential, as well as current densities and species fluxes. The inputs to the model are currently the RF power, the magnetic filter field and the source gas pressure. Results from the model are presented and where possible compared to existing experimental data from SNIF, with varying RF power, source pressure.

Dense blocks of energetic ions driven by multi-petawatt lasers

PubMed Central

Weng, S. M.; Liu, M.; Sheng, Z. M.; Murakami, M.; Chen, M.; Yu, L. L.; Zhang, J.

2016-01-01

Laser-driven ion accelerators have the advantages of compact size, high density, and short bunch duration over conventional accelerators. Nevertheless, it is still challenging to simultaneously enhance the yield and quality of laser-driven ion beams for practical applications. Here we propose a scheme to address this challenge via the use of emerging multi-petawatt lasers and a density-modulated target. The density-modulated target permits its ions to be uniformly accelerated as a dense block by laser radiation pressure. In addition, the beam quality of the accelerated ions is remarkably improved by embedding the target in a thick enough substrate, which suppresses hot electron refluxing and thus alleviates plasma heating. Particle-in-cell simulations demonstrate that almost all ions in a solid-density plasma of a few microns can be uniformly accelerated to about 25% of the speed of light by a laser pulse at an intensity around 1022 W/cm2. The resulting dense block of energetic ions may drive fusion ignition and more generally create matter with unprecedented high energy density. PMID:26924793

Electron-rich driven electrochemical solid-state amorphization in Li-Si alloys.

PubMed

Wang, Zhiguo; Gu, Meng; Zhou, Yungang; Zu, Xiaotao; Connell, Justin G; Xiao, Jie; Perea, Daniel; Lauhon, Lincoln J; Bang, Junhyeok; Zhang, Shengbai; Wang, Chongmin; Gao, Fei

2013-09-11

The physical and chemical behaviors of materials used in energy storage devices, such as lithium-ion batteries (LIBs), are mainly controlled by an electrochemical process, which normally involves insertion/extraction of ions into/from a host lattice with a concurrent flow of electrons to compensate charge balance. The fundamental physics and chemistry governing the behavior of materials in response to the ions insertion/extraction is not known. Herein, a combination of in situ lithiation experiments and large-scale ab initio molecular dynamics simulations are performed to explore the mechanisms of the electrochemically driven solid-state amorphization in Li-Si systems. We find that local electron-rich condition governs the electrochemically driven solid-state amorphization of Li-Si alloys. This discovery provides the fundamental explanation of why lithium insertion in semiconductor and insulators leads to amorphization, whereas in metals, it leads to a crystalline alloy. The present work correlates electrochemically driven reactions with ion insertion, electron transfer, lattice stability, and phase equilibrium.

Electron-Rich Driven Electrochemical Solid-State Amorphization in Li-Si Alloys

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

Wang, Zhiguo; Gu, Meng; Zhou, Yungang

2013-08-14

The physical and chemical behaviors of materials used in energy storage devices, such as lithium-ion batteries (LIBs), are mainly controlled by an electrochemical process, which normally involves insertion/extraction of ions into/from a host lattice with a concurrent flow of electrons to compensate charge balance. The fundamental physics and chemistry governing the behavior of materials in response to the ions insertion/extraction is not known. Herein, a combination of in situ lithiation experiments and large-scale ab initio molecular dynamics simulations are performed to explore the mechanisms of the electrochemically driven solid-state amorphization in Li-Si systems. We find that local electron-rich condition governsmore » the electrochemically driven solid-state amorphization of Li-Si alloys. This discovery provides the fundamental explanation of why lithium insertion in semiconductor and insulators leads to amorphization, whereas in metals, it leads to a crystalline alloy. The present work correlates electrochemically driven reactions with ion insertion, electron transfer, lattice stability and phase equilibrium.« less

Kinetic instability of electrostatic ion cyclotron waves in inter-penetrating plasmas

NASA Astrophysics Data System (ADS)

Bashir, M. F.; Ilie, R.; Murtaza, G.

2018-05-01

The Electrostatic Ion Cyclotron (EIC) instability that includes the effect of wave-particle interaction is studied owing to the free energy source through the flowing velocity of the inter-penetrating plasmas. It is shown that the origin of this current-less instability is different from the classical current driven EIC instability. The threshold conditions applicable to a wide range of plasma parameters and the estimate of the growth rate are determined as a function of the normalized flowing velocity ( u0/vt f e ), the temperature ( Tf/Ts ) and the density ratios ( nf 0/ns 0 ) of flowing component to static one. The EIC instability is driven by either flowing electrons or flowing ions, depending upon the different Doppler shifted frequency domains. It is found that the growth rate for electron-driven instability is higher than the ion-driven one. However, in both cases, the denser (hotter) is the flowing plasma, the lesser (greater) is the growth rate. The possible applications related to the terrestrial solar plasma environment are also discussed.

Global Confinement, Sawtooth Mixing, and Stochastic Diffusion Ripple Loss of Fast ICRF-driven H+ Minority Ions in TFTR

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

Petrov, M.P.; Bell, R.; Budny, R.V.

1998-07-01

This paper presents studies of ICRF-driven H+ minority ions in TFTR (Tokamak Fusion Test Reator) deuterium plasmas using primarily passive Ho flux detection in the energy range of 0.2-1.0 MeV with some corroborating active (lithium pellet charge exchange) measurements. It is shown that in the passive mode the main donors for the neutralization of H+ ions in this energy range are C5+ ions. The measured effective H+ tail temperatures range from 0.15 MeV at an ICRF power of 2 MW to 0.35 MeV at 6 MW. Analysis of the ICRF-driven H+ ion energy balance has been performed on the basismore » of the dependence of effective H+ temperatures on the plasma parameters. The analysis showed that H+ confinement times are comparable with their slowing-down times and tended to decrease with increasing ICRF power. Radial redistribution of ICRF-driven H+ ions was detected when giant sawtooth crashes occurred during the ICRF heating. The redistribution affected ions with energy below 0.7-0.8 MeV. The sawtooth crashes displace H+ ions outward along the plasma major radius into the stochastic ripple diffusion domain were those ions are lost in about 10 milliseconds. These observations are consistent with the model of the redistribution of energetic particles developed previously to explain the results of deuterium-tritium alpha-particle redistribution due to sawteeth observed in TFTR. The experimental data are also consistent with ORBIT code simulations of H+ stochastic ripple diffusion losses.« less

Review of laser-driven ion sources and their applications.

PubMed

Daido, Hiroyuki; Nishiuchi, Mamiko; Pirozhkov, Alexander S

2012-05-01

For many years, laser-driven ion acceleration, mainly proton acceleration, has been proposed and a number of proof-of-principle experiments have been carried out with lasers whose pulse duration was in the nanosecond range. In the 1990s, ion acceleration in a relativistic plasma was demonstrated with ultra-short pulse lasers based on the chirped pulse amplification technique which can provide not only picosecond or femtosecond laser pulse duration, but simultaneously ultra-high peak power of terawatt to petawatt levels. Starting from the year 2000, several groups demonstrated low transverse emittance, tens of MeV proton beams with a conversion efficiency of up to several percent. The laser-accelerated particle beams have a duration of the order of a few picoseconds at the source, an ultra-high peak current and a broad energy spectrum, which make them suitable for many, including several unique, applications. This paper reviews, firstly, the historical background including the early laser-matter interaction studies on energetic ion acceleration relevant to inertial confinement fusion. Secondly, we describe several implemented and proposed mechanisms of proton and/or ion acceleration driven by ultra-short high-intensity lasers. We pay special attention to relatively simple models of several acceleration regimes. The models connect the laser, plasma and proton/ion beam parameters, predicting important features, such as energy spectral shape, optimum conditions and scalings under these conditions for maximum ion energy, conversion efficiency, etc. The models also suggest possible ways to manipulate the proton/ion beams by tailoring the target and irradiation conditions. Thirdly, we review experimental results on proton/ion acceleration, starting with the description of driving lasers. We list experimental results and show general trends of parameter dependences and compare them with the theoretical predictions and simulations. The fourth topic includes a review of scientific, industrial and medical applications of laser-driven proton or ion sources, some of which have already been established, while the others are yet to be demonstrated. In most applications, the laser-driven ion sources are complementary to the conventional accelerators, exhibiting significantly different properties. Finally, we summarize the paper.

Overview of theory and simulations in the Heavy Ion Fusion Science Virtual National Laboratory

NASA Astrophysics Data System (ADS)

Friedman, Alex

2007-07-01

The Heavy Ion Fusion Science Virtual National Laboratory (HIFS-VNL) is a collaboration of Lawrence Berkeley National Laboratory, Lawrence Livermore National Laboratory, and Princeton Plasma Physics Laboratory. These laboratories, in cooperation with researchers at other institutions, are carrying out a coordinated effort to apply intense ion beams as drivers for studies of the physics of matter at extreme conditions, and ultimately for inertial fusion energy. Progress on this endeavor depends upon coordinated application of experiments, theory, and simulations. This paper describes the state of the art, with an emphasis on the coordination of modeling and experiment; developments in the simulation tools, and in the methods that underly them, are also treated.

X-ray crystal structure and theoretical study of a new dinuclear Cu(II) complex with two different geometry centers bridged with an oxo group

NASA Astrophysics Data System (ADS)

Golbedaghi, Reza; Azimi, Saeid; Molaei, Atefeh; Hatami, Masoud; Notash, Behrouz

2017-10-01

A new Schiff base ligand HL, 1,3-bis(2-((Z)-(2-aminoethylimino)methyl)phenoxy)ethylene di amine, has been synthesized from the reaction of a new aldehyde and ethylenediamine. After preparation the Schiff base, a new dinuclear Cu(II) complex with two different geometry for each metal ion was synthesized. Single crystal X-ray structure analysis of the complex Cu(II) showed that the complex is binuclear and all nitrogen and oxygen atoms of ligand (N4O3) are coordinated to two Cu(II) center ions. The crystal structure studying shows, a perchlorate ion has been coordinated to the two Cu(II) metal centers as bridged and another perchlorate coordinated to the one of Cu(II) ion as terminal. However, two interesting structures square pyramidal and distorted octahedral Cu(II) ions are bridged asymmetrically by a perchlorate ion and oxygen of hydroxyl group of Schiff base ligand. In addition, we had a theoretical study to have a comparison of experimental and theoretical results we determined the HOMO and LUMO orbitals.

Ion-driven deuterium permeation through tungsten at high temperatures

NASA Astrophysics Data System (ADS)

Gasparyan, Yu. M.; Golubeva, A. V.; Mayer, M.; Pisarev, A. A.; Roth, J.

2009-06-01

The ion-driven permeation (IDP) through 50 μm thick pure tungsten foils was measured in the temperature range of 823-923 K during irradiation by 200 eV/D + ion beam with a flux of 10 17-10 18 D/m 2s. Gas driven permeation (GDP) from the deuterium background gas was observed as well. Calculations using both the analytical formula for the diffusion limited regime (DLR) and the TMAP 7 code gave good agreement with the experimental data. Defects with a detrapping energy of (2.05 ± 0.15) eV were found to limit the permeation lag time in our experimental conditions.

Structure and lifetimes in ionic liquids and their mixtures.

PubMed

Gehrke, Sascha; von Domaros, Michael; Clark, Ryan; Hollóczki, Oldamur; Brehm, Martin; Welton, Tom; Luzar, Alenka; Kirchner, Barbara

2018-01-01

With the aid of molecular dynamics simulations, we study the structure and dynamics of different ionic liquid systems, with focus on hydrogen bond, ion pair and ion cage formation. To do so, we report radial distribution functions, their number integrals, and various time-correlation functions, from which we extract well-defined lifetimes by means of the reactive flux formalism. We explore the influence of polarizable force fields vs. non-polarizable ones with downscaled charges (±0.8) for the example of 1-butyl-3-methylimidazolium bromide. Furthermore, we use 1-butyl-3-methylimidazolium trifluoromethanesulfonate to investigate the impact of temperature and mixing with water as well as with the chloride ionic liquid. Smaller coordination numbers, larger distances, and tremendously accelerated dynamics are observed when the polarizable force field is applied. The same trends are found with increasing temperature. Adding water decreases the ion-ion coordination numbers whereas the water-ion and water-water coordination is enhanced. A domain analysis reveals that the nonpolar parts of the ions are dispersed and when more water is added the water clusters increase in size. The dynamics accelerate in general upon addition of water. In the ionic liquid mixture, the coordination number around the cation changes between the two anions, but the number integrals of the cation around the anions remain constant and the dynamics slow down with increasing content of the chloride ionic liquid.

The cooling of confined ions driven by laser beams

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

Reyna, L.G.; Sobehart, J.R.

1993-07-01

We finalize the dynamics of confined ions driven by a quantized radiation field. The ions can absorb photons from an incident laser beam and relax back to the ground state by either induced emissions or spontaneous emissions. Here we assume that the absorption of photons is immediately followed by spontaneous emissions, resulting in single-level ions perturbed by the exchange of momentum with the radiation field. The probability distribution of the ions is calculated using singular expansions in the low noise asymptotic limit. The present calculations reproduce the quantum results in the limit of heavy particles in static traps, and themore » classical results of ions in radio-frequency confining wells.« less

Nonlinear structure formation in ion-temperature-gradient driven drift waves in pair-ion plasma with nonthermal electron distribution

NASA Astrophysics Data System (ADS)

Razzaq, Javaria; Haque, Q.; Khan, Majid; Bhatti, Adnan Mehmood; Kamran, M.; Mirza, Arshad M.

2018-02-01

Nonlinear structure formation in ion-temperature-gradient (ITG) driven waves is investigated in pair-ion plasma comprising ions and nonthermal electrons (kappa, Cairns). By using the transport equations of the Braginskii model, a new set of nonlinear equations are derived. A linear dispersion relation is obtained and discussed analytically as well as numerically. It is shown that the nonthermal population of electrons affects both the linear and nonlinear characteristics of the ITG mode in pair-ion plasma. This work will be useful in tokamaks and stellarators where non-Maxwellian population of electrons may exist due to resonant frequency heating, electron cyclotron heating, runaway electrons, etc.

Ion sound instability driven by the ion flows

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

Koshkarov, O., E-mail: koshkarov.alexandr@usask.ca; Smolyakov, A. I.; National Research Centre

2015-05-15

Ion sound instabilities driven by the ion flow in a system of a finite length are considered by analytical and numerical methods. The ion sound waves are modified by the presence of stationary ion flow resulting in negative and positive energy modes. The instability develops due to coupling of negative and positive energy modes mediated by reflections from the boundary. It is shown that the wave dispersion due to deviation from quasineutrality is crucial for the stability. In finite length system, the dispersion is characterized by the length of the system measured in units of the Debye length. The instabilitymore » is studied analytically and the results are compared with direct, initial value numerical simulations.« less

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

Chumakov, Yu. M.; Paholnitcaia, A. Yu.; Petrenko, P. A.

Two crystal modifications of nitrato-(2-[2-(1-pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazolo) aquacopper (I and II) and two modifications of chloro-(2-[2-phenyl(pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazolo) copper (III and IV) have been synthesized and studied by X-ray diffraction. In structures I and II, the copper atoms coordinate a monodeprotonated molecule of the organic ligand, nitrate ions, and a water molecule. In crystals of I, the complexes are monomeric, whereas complexes II are linked via nitrate ions to form polymeric chains. In both structures the coordination polyhedron of the copper atom can be described as a distorted tetragonal bipyramid—(4 + 1 + 1) in I and (4 + 2) in II. These coordinationmore » polyherdra have different compositions. In structures III and IV, the metal atoms coordinate a monodeprotonated (2-[2-phenyl(pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazole molecule and chloride ions. In III the complex-forming ion has square-planar coordination geometry, whereas structure IV consists of centrosymmetric dimers with two bridging chlorine atoms. It was found that nitrato-(2-[2-(1-pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazolo) aquacopper possesses antitumor activity.« less

Gyrokinetic stability of electron-positron-ion plasmas

NASA Astrophysics Data System (ADS)

Mishchenko, A.; Zocco, A.; Helander, P.; Könies, A.

2018-02-01

The gyrokinetic stability of electron-positron plasmas contaminated by an ion (proton) admixture is studied in a slab geometry. The appropriate dispersion relation is derived and solved. Stable K-modes, the universal instability, the ion-temperature-gradient-driven instability, the electron-temperature-gradient-driven instability and the shear Alfvén wave are considered. It is found that the contaminated plasma remains stable if the contamination degree is below some threshold and that the shear Alfvén wave can be present in a contaminated plasma in cases where it is absent without ion contamination.

Stoichiometric control of multiple different tectons in coordination-driven self-assembly: preparation of fused metallacyclic polygons.

PubMed

Lee, Junseong; Ghosh, Koushik; Stang, Peter J

2009-09-02

We present a general strategy for the synthesis of stable, multicomponent fused polygon complexes in which coordination-driven self-assembly allows for single supramolecular species to be formed from multicomponent self-assembly and the shape of the obtained polygons can be controlled simply by changing the ratio of individual components. The compounds have been characterized by multinuclear NMR spectroscopy and electrospray ionization mass spectrometry.

N-donor co-ligands driven two new Co(II)- coordination polymers with bi- and trinuclear units: Crystal structures, and magnetic properties

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

Zhou, Zhi-Hang; Han, Min-Le; Wu, Ya-Pan

2016-10-15

Two new Co(II) coordination polymers(CPs), namely [Co{sub 2}(bpe){sub 2}(Hbppc)]{sub n} (1) and [Co{sub 3}(μ{sub 3}-OH)(bppc)(bpm)(H{sub 2}O)]·3H{sub 2}O (2) (H{sub 5}bppc=biphenyl-2,4,6,3′,5′-pentacarboxylic acid, bpe=1,2-bis(4-pyridyl)ethene, bpm=bis(4-pyridyl)amine), have been obtained and characterized by elemental analysis, single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), IR spectra and thermogravimetric analysis (TGA). 1 shows a binodal (4,6)-connected fsc net with a (4{sup 4}·6{sup 10}·8)(4{sup 4}·6{sup 2}) topology, while 2 shows a binodal (5,7)-connected 3D network based on trinuclear [Co{sub 3}(μ{sub 3}-OH)]{sup 5+} units with unusual (3.4{sup 6}.5{sup 2}.6)(3{sup 2}.4{sup 6}.5{sup 7}.6{sup 5}.7) topology. Variable-temperature magnetic susceptibility measurements reveals that complex 1 shows ferromagnetic interactions between the adjacent Co(II)more » ions, whereas 2 is a antiferromagnetic system. - Graphical abstract: Two new Co(II) coordination polymers with bi- and trinuclear units have been obtained. 1 shows a binodal (4,6)-connected fsc net with a (4{sup 4}·6{sup 10}·8)(4{sup 4}·6{sup 2}) topology and antiferromagnetic interactions between the adjacent Co(II) ions, while 2 is a binodal (5,7)-connected 3D network with unusual (3.4{sup 6}.5{sup 2}.6)(3{sup 2}.4{sup 6}.5{sup 7}.6{sup 5}.7) topology and a ferromagnetic system. - Highlights: • Two Co(II) coordination polymers with different multimetallic clusters as building units. • A (4,6)-connected fsc net and a (5,7)-connected 3D network. • A antiferromagnetic coupling for 1 and A ferromagnetic coupling for 2.« less

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

Park, Jinhee; Chen, Ying-Pin; Perry, Zachary

A series of molybdenum- and copper-based MOPs were synthesized through coordination-driven process of a bridging ligand (3,3 -PDBAD, L1) and dimetal paddlewheel clusters. Three conformers of the ligand exist with an ideal bridging angle between the two carboxylate groups of 0° (H2α-L1), 120° (H2β-L1), and of 90° (H2γ-L1), respectively. At ambient or lower temperature, H2L1 and Mo2(OAc)4 or Cu2(OAc)4 were crystallized into a molecular square with γ-L1 and Mo2/Cu2 units. With proper temperature elevation, not only the molecular square with γ-L1 but also a lantern-shaped cage with α-L1 formed simultaneously. Similar to how Watson–Crick pairs stabilize the helical structure ofmore » duplex DNA, the core–shell molecular assembly possesses favorable H-bonding interaction sites. This is dictated by the ligand conformation in the shell, coding for the formation and providing stabilization of the central lantern shaped core, which was not observed without this complementary interaction. On the basis of the crystallographic implications, a heterobimetallic cage was obtained through a postsynthetic metal ion metathesis, showing different reactivity of coordination bonds in the core and shell. As an innovative synthetic strategy, the site-selective metathesis broadens the structural diversity and properties of coordination assemblies.« less

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

Park, J; Chen, YP; Perry, Z

A series of molybdenum- and copper-based MOPs were synthesized through coordination-driven process of a bridging ligand (3,3'-PDBAD, L-1) and dimetal paddlewheel clusters. Three conformers of the ligand exist with an ideal bridging angle between the two carboxylate groups of 0 degrees (H-2 zeta-L(1)), 120 degrees (H-2 beta-L-1), and of 90 degrees (H-2 beta-L-1), respectively. At ambient or lower temperature, (HL1)-L-2 and Mo-2(OAc)(4) or Cu-2(OAc)(4) were crystallized into a molecular square with ?-L-1 and Mo-2/Cu-2 units. With proper temperature elevation, not only the molecular square with ?-L-1 but also a lantern-shaped cage with a-L-1 formed simultaneously. Similar to how Watson-Crick pairsmore » stabilize the helical structure of duplex DNA, the core-shell molecular assembly possesses favorable H-bonding interaction sites. This is dictated by the ligand conformation in the shell, coding for the formation and providing stabilization of the central lantern shaped core, which was not observed without this complementary interaction. On the basis of the crystallographic implications, a heterobimetallic cage was obtained through a postsynthetic metal ion metathesis, showing different reactivity of coordination bonds in the core and shell. As an innovative synthetic strategy, the site-selective metathesis broadens the structural diversity and properties of coordination assemblies.« less

Variation of the coordination environment and its effect on the white light emission properties in a Mn-doped ZnO-ZnS complex structure.

PubMed

Cheng, Yan; Chen, Rui; Feng, Haifeng; Hao, Weichang; Xu, Huaizhe; Wang, Yu; Li, Jiong

2014-03-14

Mn-doped ZnO-ZnS complex nanocrystals were fabricated through coating of dodecanethiol on Mn-doped ZnO nanocrystals. The relationship between the component of white light emission and the coordination environments of Mn-dopants were experimentally investigated. It was shown that Mn ions mainly formed Mn(3+)O6 octahedra in as prepared Mn-doped ZnO, while the Mn(3+) ions on the surface of ZnO transferred into Mn(2+) ions at the interface between ZnO and ZnS after dodecanethiol coating. The Mn(2+)S4 tetrahedron density and the orange emission intensity increased upon enhancing the dodecanethiol content. These results provide an alternative way to optimize the white emission spectrum from nanocrystals of Mn-doped ZnS-ZnO complex structures through modulation of the coordination environment of Mn ions.

Synthesis, structure, spectroscopic and electrochemical properties of (2-amino-4-methylpyrimidine)-(pyridine-2,6-dicarboxylato)copper(II) monohydrate

NASA Astrophysics Data System (ADS)

Uçar, İbrahim; Karabulut, Bünyamin; Bulut, Ahmet; Büyükgüngör, Orhan

2007-05-01

The (2-amino-4-methylpyrimidine)-(pyridine-2,6-dicarboxylato)copper(II) monohydrate complex was synthesized and characterized by spectroscopic (IR, UV/Vis, EPR), thermal (TG/DTA) and electrochemical methods. X-ray structural analysis of the title complex revealed that the copper ion can be considered to have two coordination spheres. In the first coordination sphere the copper ion forms distorted square-planar geometry with trans-N 2O 2 donor set, and also the metal ion is weakly bonded to the amino-nitrogen in the layer over and to the carboxylic oxygen in the layer underneath in the second coordination sphere. The second coordination environment on the copper ion is attributed to pseudo octahedron. The powder EPR spectra of Cu(II) complex at room and liquid nitrogen temperature were recorded. The calculated g and A parameters have indicated that the paramagnetic centre is axially symmetric. The molecular orbital bond coefficients of the Cu(II) ion in d 9 state is also calculated by using EPR and optical absorption parameters. The cyclic voltammogram of the title complex investigated in DMSO (dimethylsulfoxide) solution exhibits only metal centered electroactivity in the potential range -1.25 to 1.5 V versus Ag/AgCl reference electrode.

Solvation of actinide salts in water using a polarizable continuum model.

PubMed

Kumar, Narendra; Seminario, Jorge M

2015-01-29

In order to determine how actinide atoms are dressed when solvated in water, density functional theory calculations have been carried out to study the equilibrium structure of uranium plutonium and thorium salts (UO2(2+), PuO2(2+), Pu(4+), and Th(4+)) both in vacuum as well as in solution represented by a conductor-like polarizable continuum model. This information is of paramount importance for the development of sensitive nanosensors. Both UO2(2+) and PuO2(2+) ions show coordination number of 4-5 with counterions replacing one or two water molecules from the first coordination shell. On the other hand, Pu(4+), has a coordination number of 8 both when completely solvated and also in the presence of chloride and nitrate ions with counterions replacing water molecules in the first shell. Nitrates were found to bind more strongly to Pu(IV) than chloride anions. In the case of the Th(IV) ion, the coordination number was found to be 9 or 10 in the presence of chlorides. Moreover, the Pu(IV) ion shows greater affinity for chlorides than the Th(IV) ion. Adding dispersion and ZPE corrections to the binding energy does not alter the trends in relative stability of several conformers because of error cancelations. All structures and energetics of these complexes are reported.

ESR, spectroscopic, and quantum-chemical studies on the electronic structures of complexes formed by Cu(I) with radicals (in Russian)

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

Gritsan, N.P.; Usov, O.M.; Shokhirev, N.V.

1986-07-01

The optical and ESR spectra have been examined for complexes of Cu(I) with various radicals, which contain various numbers of Cl/sup -/ ions in the central-atom coordination sphere. The spin-Hamiltonian parameters have been determined for all these radical complexes, and the observed ESR spectra have been compared with those calculated with allowance for second-order effects. The observed values for the isotropic and anisotropic components of the HFI constant from the central ion have been used to estimate the contributions from the 4s and 3d/sup 2//sub z/ orbitals of the copper ion to the unpaired-electron MO. Quantum-chemical calculations have been performedmore » by the INDO method on the electronic structures and geometries of complexes formed by CH/sub 2/OH with Cu(I) for various Cl/sup -/ contents in the coordination sphere. The radical is coordinated by the ..pi.. orbital on the carbon atom, and the stabilities of the radical complexes decrease as the number of Cl/sup -/ ions in the coordination sphere increases. A geometry close to planar for the CuCl/sub 4//sup 3 -/ fragment in a complex containing four Cl/sup -/ ions.« less

Modeling of the control of the driven current profile in ICRF MCCD on EAST plasma

NASA Astrophysics Data System (ADS)

Yin, L.; Yang, C.; Gong, X. Y.; Lu, X. Q.; Cao, J. J.; Wu, Z. Y.; Chen, Y.; Du, D.

2018-05-01

Control of the current profile is a crucial issue for improved confinement and the inhibition of instability in advanced tokamak operation. Using typical discharge data for the Experimental Advanced Superconducting Tokamak, numerical simulations of driven-current profile control in mode conversion current drive (MCCD) in the ion cyclotron range of frequencies were performed employing a full-wave method and Ehst-Karney efficiency formula. Results indicate that the driven current profile in MCCD can be effectively modified by shifting the mode conversion layer. The peak of the driven current can be located at an aimed position in the normalized minor radius range (-0.60 ≤r/a≤0) by changing the radiofrequency and the minority-ion concentration. The efficiency of the off-axis MCCD can reach 233 kA/MW through optimization, and the mode converted ion cyclotron wave plays an important role in such scenarios. The effects of electron temperature and plasma density on the driven current profile are also investigated.

The open gate of the K(V)1.2 channel: quantum calculations show the key role of hydration.

PubMed

Kariev, Alisher M; Njau, Philipa; Green, Michael E

2014-02-04

The open gate of the Kv1.2 voltage-gated potassium channel can just hold a hydrated K(+) ion. Quantum calculations starting from the x-ray coordinates of the channel confirm this, showing little change from the x-ray coordinates for the protein. Water molecules not in the x-ray coordinates, and the ion itself, are placed by the calculation. The water molecules, including their orientation and hydrogen bonding, with and without an ion, are critical for the path of the ion, from the solution to the gate. A sequence of steps is postulated in which the potential experienced by the ion in the pore is influenced by the position of the ion. The gate structure, with and without the ion, has been optimized. The charges on the atoms and bond lengths have been calculated using natural bond orbital calculations, giving K(+) ~0.77 charges, rather than 1.0. The PVPV hinge sequence has been mutated in silico to PVVV (P407V in the 2A79 numbering). The water structure around the ion becomes discontinuous, separated into two sections, above and below the ion. PVPV conservation closely relates to maintaining the water structure. Finally, these results have implications concerning gating. Copyright © 2014 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Clarification of the binding model of lead(II) with a highly sensitive and selective fluoroionophore sensor by spectroscopic and structural study

NASA Astrophysics Data System (ADS)

Ma, Lijun; Li, Yue; Li, Lei; Wu, Yuqing; Buchet, Rene; Ding, Yihong

2009-03-01

The detection of lead ion is very important both in environment and in biological systems because of its toxicity. A fluoroionophore sensor, N-[4(1-pyrene)-butyroyl]- L-tryptophan (PLT), distinguishing Pb 2+ from other 12 metal ions and exhibiting a very high sensitivity (0.15 μM) in aqueous solution, has been reported. The present study describes the spectroscopic clarification of the intrinsic differences of the binding model between PLT with Pb 2+ and with other ions. The fluorescent property of solid metal carboxylates reflects a character of the metal complex in solution, which results in a facility to solve problems by using solid sample of complex and vibrational spectroscopy. Both FT-infrared and Raman spectroscopy are employed to clarify the binding model between lead ion and its high sensitive and selective fluoroionophore sensor PLT, and essentially to explain why the metal ions other than Pb 2+ cannot response to PLT. The IR spectral data clearly show that a bridging bidentate coordination occurs when PLT is coordinated with Cu 2+ and Zn 2+; while a chelating bidentate coordination between the carboxyl anion and Pb 2+ exists in PLT-Pb, which is a new information beyond the NMR results in previous report. Meanwhile, the present study also indicates a characteristic interaction of lead ion and indole ring as well as the hydrogen bonding between amide groups. Furthermore, the quantum chemical calculations at the DFT level confirm the spectral and structural information of PLT-Pb 2+ proposed by experiments. Thus, the type of coordination, the interaction of the indole ring with the metal ion, and the hydrogen bonding between amide groups in PLT-Pb are likely responsible for the high selectivity of PLT to the lead(II) ion.

Clarification of the binding model of lead(II) with a highly sensitive and selective fluoroionophore sensor by spectroscopic and structural study.

PubMed

Ma, Lijun; Li, Yue; Li, Lei; Wu, Yuqing; Buchet, Rene; Ding, Yihong

2009-03-01

The detection of lead ion is very important both in environment and in biological systems because of its toxicity. A fluoroionophore sensor, N-[4(1-pyrene)-butyroyl]-l-tryptophan (PLT), distinguishing Pb(2+) from other 12 metal ions and exhibiting a very high sensitivity (0.15microM) in aqueous solution, has been reported. The present study describes the spectroscopic clarification of the intrinsic differences of the binding model between PLT with Pb(2+) and with other ions. The fluorescent property of solid metal carboxylates reflects a character of the metal complex in solution, which results in a facility to solve problems by using solid sample of complex and vibrational spectroscopy. Both FT-infrared and Raman spectroscopy are employed to clarify the binding model between lead ion and its high sensitive and selective fluoroionophore sensor PLT, and essentially to explain why the metal ions other than Pb(2+) cannot response to PLT. The IR spectral data clearly show that a bridging bidentate coordination occurs when PLT is coordinated with Cu(2+) and Zn(2+); while a chelating bidentate coordination between the carboxyl anion and Pb(2+) exists in PLT-Pb, which is a new information beyond the NMR results in previous report. Meanwhile, the present study also indicates a characteristic interaction of lead ion and indole ring as well as the hydrogen bonding between amide groups. Furthermore, the quantum chemical calculations at the DFT level confirm the spectral and structural information of PLT-Pb(2+) proposed by experiments. Thus, the type of coordination, the interaction of the indole ring with the metal ion, and the hydrogen bonding between amide groups in PLT-Pb are likely responsible for the high selectivity of PLT to the lead(II) ion.

Controllable robust laser driven ion acceleration from near-critical density relativistic self-transparent plasma

NASA Astrophysics Data System (ADS)

Liu, Bin; Meyer-Ter-Vehn, Juergen; Ruhl, Hartmut

2017-10-01

We introduce an alternative approach for laser driven self-injected high quality ion acceleration. We call it ion wave breaking acceleration. It operates in relativistic self-transparent plasma for ultra-intense ultra-short laser pulses. Laser propagating in a transparent plasma excites an electron wave as well as an ion wave. When the ion wave breaks, a fraction of ions is self-injected into the positive part of the laser driven wake. This leads to a superior ion pulse with peaked energy spectra; in particular in realistic three-dimensional geometry, the injection occurs localized close to the laser axis producing highly directed bunches. A theory is developed to investigate the ion wave breaking dynamics. Three dimensional Particle-in-Cell simulations with pure-gaussian laser pulses and pre-expanded near-critical density plasma targets have been done to verify the theoretical results. It is shown that hundreds of MeV, easily controllable and manipulable, micron-scale size, highly collimated and quasi-mono-energetic ion beams can be produced by using ultra-intense ultra-short laser pulses with total laser energies less than 10 Joules. Such ion beams may find important applications in tumour therapy. B. Liu acknowledges support from the Alexander von Humboldt Foundation. B. Liu and H. Ruhl acknowledge supports from the Gauss Centre for Supercomputing (GCS), and the Cluster-of-Excellence Munich Centre for Advanced Photonics (MAP).

A CW radiofrequency ion source for production of negative hydrogen ion beams for cyclotrons

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

Kalvas, T.; Tarvainen, O.; Komppula, J.

2015-04-08

A CW 13.56 MHz radiofrequency-driven ion source RADIS for production of H{sup −} and D{sup −} beams is under development for replacing the filament-driven ion source of the MCC30/15 cyclotron. The RF ion source has a 16-pole multicusp plasma chamber, an electromagnet-based magnetic filter and an external planar spiral RF antenna behind an AlN window. The extraction is a 5-electrode system with an adjustable puller electrode voltage for optimizing the beam formation, a water-cooled electron dump electrode and an accelerating einzel lens. At 2650 W of RF power, the source produces 1 mA of H{sup −} (2.6 mA/cm{sup 2}), which is the intensity neededmore » at injection for production of 200 µA H{sup +} with the filament-driven ion source. A simple pepperpot device has been developed for characterizing the beam emittance. Plans for improving the power efficiency with the use of a new permanent magnet front plate is discussed.« less

The formation and dissipation of electrostatic shock waves: the role of ion–ion acoustic instabilities

NASA Astrophysics Data System (ADS)

Zhang, Wen-shuai; Cai, Hong-bo; Zhu, Shao-ping

2018-05-01

The role of ion–ion acoustic instabilities in the formation and dissipation of collisionless electrostatic shock waves driven by counter-streaming supersonic plasma flows has been investigated via two-dimensional particle-in-cell simulations. The nonlinear evolution of unstable waves and ion velocity distributions has been analyzed in detail. It is found that for electrostatic shocks driven by moderate-velocity flows, longitudinal and oblique ion–ion acoustic instabilities can be excited in the downstream and upstream regions, which lead to thermalization of the transmitted and reflected ions, respectively. For high-velocity flows, oblique ion–ion acoustic instabilities can develop in the overlap layer during the shock formation process and impede the shock formation.

Structural effects of Cu(II)-coordination in the octapeptide region of the human prion protein.

PubMed

Riihimäki, Eva-Stina; Martínez, José Manuel; Kloo, Lars

2008-05-14

The copper-binding ability of the prion protein is thought to be central to its function. The structural effects of copper coordination in the octapeptide region of the human prion protein have been investigated by molecular dynamics simulations. Simulations were performed with the apo state, in order to investigate the behavior of the region without copper ions, as well as with the octapeptide region in the presence of copper ions. While the structure of the apo state is greatly influenced by the interaction between the rings in the histidine, tryptophan and proline residues, the region shows evidence of highly ordered coordination sites in the presence of copper ions. The position of the tryptophan indole ring is stabilized by cation-pi interactions. Two stable orientations of the indole ring with respect to the equatorial coordination plane of copper were observed, which showed that the indole ring can reside on both sides of the coordination plane. The interaction with the indole ring was found to occur without a mediating axial water molecule.

Recent progress of the Laser-driven Ion-beam Trace Probe

NASA Astrophysics Data System (ADS)

Yang, Xiaoyi; Xiao, Chijie; Chen, Yihang; Xu, Tianchao; Yu, Yi; Xu, Min; Wang, Long; Lin, Chen; Wang, Xiaogang

2017-10-01

The Laser-driven Ion-beam Trace Probe (LITP) is a new method to diagnose the poloidal magnetic field and radial electric field in tokamaks. Recently significant progresses have been made as follows. 1) The experimental system has been set up on the PKU Plasma Test (PPT) linear device and begun to validate the principle of LITP, including the ion source, the ion detector and the poloidal magnetic field cable. Preliminary experimental results matched the theoretical prediction well. 2) The reconstruction principle has been improved including the nonlinear effect. 3) Tomography methods have been applied in the reconstruction codes. Now the laser-driven ion-beam accelerator has been setup on the PPT device, and further test of LITP will start soon. After that a prototype of LITP system will be designed and setup on the HL-2A tokamak device. This work was supported by the CHINA MOST under 2012YQ030142, ITER-CHINA program 2015GB120001 and National Natural Science Foundation of China under 11575014 and 11375053.

Robust ion current oscillations under a steady electric field: An ion channel analog.

PubMed

Yan, Yu; Wang, Yunshan; Senapati, Satyajyoti; Schiffbauer, Jarrod; Yossifon, Gilad; Chang, Hsueh-Chia

2016-08-01

We demonstrate a nonlinear, nonequilibrium field-driven ion flux phenomenon, which unlike Teorell's nonlinear multiple field theory, requires only the application of one field: robust autonomous current-mass flux oscillations across a porous monolith coupled to a capillary with a long air bubble, which mimics a hydrophobic protein in an ion channel. The oscillations are driven by the hysteretic wetting dynamics of the meniscus when electro-osmotic flow and pressure driven backflow, due to bubble expansion, compete to approach zero mass flux within the monolith. Delayed rupture of the film around the advancing bubble cuts off the electric field and switches the monolith mass flow from the former to the latter. The meniscus then recedes and repairs the rupture to sustain an oscillation for a range of applied fields. This generic mechanism shares many analogs with current oscillations in cell membrane ion channel. At sufficiently high voltage, the system undergoes a state transition characterized by appearance of the ubiquitous 1/f power spectrum.

Electrostatic waves driven by electron beam in lunar wake plasma

NASA Astrophysics Data System (ADS)

Sreeraj, T.; Singh, S. V.; Lakhina, G. S.

2018-05-01

A linear analysis of electrostatic waves propagating parallel to the ambient field in a four component homogeneous, collisionless, magnetised plasma comprising fluid protons, fluid He++, electron beam, and suprathermal electrons following kappa distribution is presented. In the absence of electron beam streaming, numerical analysis of the dispersion relation shows six modes: two electron acoustic modes (modes 1 and 6), two fast ion acoustic modes (modes 2 and 5), and two slow ion acoustic modes (modes 3 and 4). The modes 1, 2 and 3 and modes 4, 5, and 6 have positive and negative phase speeds, respectively. With an increase in electron beam speed, the mode 6 gets affected the most and the phase speed turns positive from negative. The mode 6 thus starts to merge with modes 2 and 3 and generates the electron beam driven fast and slow ion acoustic waves unstable with a finite growth. The electron beam driven slow ion-acoustic waves occur at lower wavenumbers, whereas fast ion-acoustic waves occur at a large value of wavenumbers. The effect of various other parameters has also been studied. We have applied this analysis to the electrostatic waves observed in lunar wake during the first flyby of the ARTEMIS mission. The analysis shows that the low (high) frequency waves observed in the lunar wake could be the electron beam driven slow (fast) ion-acoustic modes.

Time of Flight based diagnostics for high energy laser driven ion beams

NASA Astrophysics Data System (ADS)

Scuderi, V.; Milluzzo, G.; Alejo, A.; Amico, A. G.; Booth, N.; Cirrone, G. A. P.; Doria, D.; Green, J.; Kar, S.; Larosa, G.; Leanza, R.; Margarone, D.; McKenna, P.; Padda, H.; Petringa, G.; Pipek, J.; Romagnani, L.; Romano, F.; Schillaci, F.; Borghesi, M.; Cuttone, G.; Korn, G.

2017-03-01

Nowadays the innovative high power laser-based ion acceleration technique is one of the most interesting challenges in particle acceleration field, showing attractive characteristics for future multidisciplinary applications, including medical ones. Nevertheless, peculiarities of optically accelerated ion beams make mandatory the development of proper transport, selection and diagnostics devices in order to deliver stable and controlled ion beams for multidisciplinary applications. This is the main purpose of the ELIMAIA (ELI Multidisciplinary Applications of laser-Ion Acceleration) beamline that will be realized and installed within 2018 at the ELI-Beamlines research center in the Czech Republic, where laser driven high energy ions, up to 60 MeV/n, will be available for users. In particular, a crucial role will be played by the on-line diagnostics system, recently developed in collaboration with INFN-LNS (Italy), consisting of TOF detectors, placed along the beamline (at different detection distances) to provide online monitoring of key characteristics of delivered beams, such as energy, fluence and ion species. In this contribution an overview on the ELIMAIA available ion diagnostics will be briefly given along with the preliminary results obtained during a test performed with high energy laser-driven proton beams accelerated at the VULCAN PW-laser available at RAL facility (U.K.).

Bond-length distributions for ions bonded to oxygen: alkali and alkaline-earth metals.

PubMed

Gagné, Olivier Charles; Hawthorne, Frank Christopher

2016-08-01

Bond-length distributions have been examined for 55 configurations of alkali-metal ions and 29 configurations of alkaline-earth-metal ions bonded to oxygen, for 4859 coordination polyhedra and 38 594 bond distances (alkali metals), and for 3038 coordination polyhedra and 24 487 bond distances (alkaline-earth metals). Bond lengths generally show a positively skewed Gaussian distribution that originates from the variation in Born repulsion and Coulomb attraction as a function of interatomic distance. The skewness and kurtosis of these distributions generally decrease with increasing coordination number of the central cation, a result of decreasing Born repulsion with increasing coordination number. We confirm the following minimum coordination numbers: ([3])Li(+), ([3])Na(+), ([4])K(+), ([4])Rb(+), ([6])Cs(+), ([3])Be(2+), ([4])Mg(2+), ([6])Ca(2+), ([6])Sr(2+) and ([6])Ba(2+), but note that some reported examples are the result of extensive dynamic and/or positional short-range disorder and are not ordered arrangements. Some distributions of bond lengths are distinctly multi-modal. This is commonly due to the occurrence of large numbers of structure refinements of a particular structure type in which a particular cation is always present, leading to an over-representation of a specific range of bond lengths. Outliers in the distributions of mean bond lengths are often associated with anomalous values of atomic displacement of the constituent cations and/or anions. For a sample of ([6])Na(+), the ratio Ueq(Na)/Ueq(bonded anions) is partially correlated with 〈([6])Na(+)-O(2-)〉 (R(2) = 0.57), suggesting that the mean bond length is correlated with vibrational/displacement characteristics of the constituent ions for a fixed coordination number. Mean bond lengths also show a weak correlation with bond-length distortion from the mean value in general, although some coordination numbers show the widest variation in mean bond length for zero distortion, e.g. Li(+) in [4]- and [6]-coordination, Na(+) in [4]- and [6]-coordination. For alkali-metal and alkaline-earth-metal ions, there is a positive correlation between cation coordination number and the grand mean incident bond-valence sum at the central cation, the values varying from 0.84 v.u. for ([5])K(+) to 1.06 v.u. for ([8])Li(+), and from 1.76 v.u. for ([7])Ba(2+) to 2.10 v.u. for ([12])Sr(2+). Bond-valence arguments suggest coordination numbers higher than [12] for K(+), Rb(+), Cs(+) and Ba(2+).

Further insights into the metal ion binding abilities and the metalation pathway of a plant metallothionein from Musa acuminata

PubMed Central

Cabral, Augusto C. S.; Jakovleska, Jovana; Deb, Aniruddha; Penner-Hahn, James E.; Pecoraro, Vincent L.

2017-01-01

The superfamily of metallothioneins (MTs) combines a diverse group of metalloproteins, sharing the characteristics of rather low molecular weight and high cysteine content. The latter provides MTs with the capability to coordinate thiophilic metal ions, in particular those with a d10 electron configuration. The sub-family of plant MT3 proteins is only poorly characterized and there is a complete lack of three-dimensional structure information. Building upon our previous results on the Musa acuminata MT3 (musMT3) protein, the focus of the present work is to understand the metal cluster formation process, the role of the single histidine residue present in musMT3, and the metal ion binding affinity. We concentrate our efforts on the coordination of ZnII and CdII ions, using CoII as a spectroscopic probe for ZnII binding. The overall protein-fold is analysed with a combination of limited proteolytic digestion, mass spectrometry, and dynamic light scattering. Histidine coordination of metal ions is probed with extended X-ray absorption fine structure spectroscopy and CoII titration experiments. Initial experiments with isothermal titration calorimetry provide insights into the thermodynamics of metal ion binding. PMID:29218632

Combined distribution functions: A powerful tool to identify cation coordination geometries in liquid systems

NASA Astrophysics Data System (ADS)

Sessa, Francesco; D'Angelo, Paola; Migliorati, Valentina

2018-01-01

In this work we have developed an analytical procedure to identify metal ion coordination geometries in liquid media based on the calculation of Combined Distribution Functions (CDFs) starting from Molecular Dynamics (MD) simulations. CDFs provide a fingerprint which can be easily and unambiguously assigned to a reference polyhedron. The CDF analysis has been tested on five systems and has proven to reliably identify the correct geometries of several ion coordination complexes. This tool is simple and general and can be efficiently applied to different MD simulations of liquid systems.

EVIDENCE FOR PHOTOIONIZATION-DRIVEN BROAD ABSORPTION LINE VARIABILITY

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

Wang, Tinggui; Yang, Chenwei; Wang, Huiyuan

2015-12-01

We present a qualitative analysis of the variability of quasar broad absorption lines using the large multi-epoch spectroscopic data set of the Sloan Digital Sky Survey Data Release 10. We confirm that variations of absorption lines are highly coordinated among different components of the same ion or the same absorption component of different ions for C iv, Si iv, and N v. Furthermore, we show that the equivalent widths (EWs) of the lines decrease or increase statistically when the continuum brightens or dims. This is further supported by the synchronized variations of emission and absorption-line EWs when the well-established intrinsicmore » Baldwin effect for emission lines is taken into account. We find that the emergence of an absorption component is usually accompanied by the dimming of the continuum while the disappearance of an absorption-line component is accompanied by the brightening of the continuum. This suggests that the emergence or disappearance of a C iv absorption component is only the extreme case, when the ionic column density is very sensitive to continuum variations or the continuum variability the amplitude is larger. These results support the idea that absorption-line variability is driven mainly by changes in the gas ionization in response to continuum variations, that the line-absorbing gas is highly ionized, and in some extreme cases, too highly ionized to be detected in UV absorption lines. Due to uncertainties in the spectroscopic flux calibration, we cannot quantify the fraction of quasars with asynchronized continuum and absorption-line variations.« less

New water soluble heterometallic complex showing unpredicted coordination modes of EDTA

NASA Astrophysics Data System (ADS)

Mudsainiyan, R. K.; Jassal, A. K.; Chawla, S. K.

2015-10-01

A mesoporous 3D polymeric complex (I) having formula {[Zr(IV)O-μ3-(EDTA)Fe(III)OH]·H2O}n has been crystallized and characterized by various techniques. Single-crystal X-ray diffraction analysis revealed that complex (I) crystallized in chiral monoclinic space group Cc (space group no. 9) with unexpected coordination modes of EDTA and mixture of two transition metal ions. In this complex, the coordination number of Zr(IV) ion is seven where four carboxylate oxygen atoms, two nitrogen atoms, one oxide atom are coordinating with Zr(IV). Fe(III) is four coordinated and its coordination environment is composed of three different carboxylic oxygen atoms from three different EDTA and one oxygen atom of -OH group. The structure consists of 4-c and 16-c (2-nodal) net with new topology and point symbol for net is (336·454·530)·(36). TGA study and XRPD pattern showed that the coordination polymer is quite stable even after losing water molecule and -OH ion. Quenching behavior in fluorescence of ligand is observed by complexation with transition metal ions is due to n-π* transition. The SEM micrograph shows the morphology of complex (I) exhibits spherical shape with size ranging from 50 to 280 nm. The minimum N2 (SBET=8.7693 m2/g) and a maximum amount of H2 (high surface area=1044.86 m2/g (STP)) could be adsorbed at 77 K. From DLS study, zeta potential is calculated i.e. -7.94 shows the negative charges on the surface of complex. Hirshfeld surface analysis and fingerprint plots revealed influence of weak or non bonding interactions in crystal packing of complex.

Modeling of fast neutral-beam-generated ions and rotation effects on RWM stability in DIII-D plasmas

DOE PAGES

Turco, Francesca; Turnbull, Alan D.; Hanson, Jeremy M.; ...

2015-10-15

Here, validation results for the MARS-K code for DIII-D equilibria, predict that the absence of fast Neutral Beam (NB) generated ions leads to a plasma response ~40–60% higher than in NB-sustained H-mode plasmas when the no-wall β N limit is reached. In a β N scan, the MARS-K model with thermal and fast-ions, reproduces the experimental measurements above the no-wall limit, except at the highest β N where the phase of the plasma response is overestimated. The dependencies extrapolate unfavorably to machines such as ITER with smaller fast ion fractions since elevated responses in the absence of fast ions indicatemore » the potential onset of a resistive wall mode (RWM). The model was also tested for the effects of rotation at high β N, and recovers the measured response even when fast-ions are neglected, reversing the effect found in lower β N cases, but consistent with the higher β N results above the no-wall limit. The agreement in the response amplitude and phase for the rotation scan is not as good, and additional work will be needed to reproduce the experimental trends. In the case of current-driven instabilities, the magnetohydrodynamic spectroscopy system used to measure the plasma response reacts differently from that for pressure driven instabilities: the response amplitude remains low up to ~93% of the current limit, showing an abrupt increase only in the last ~5% of the current ramp. This makes it much less effective as a diagnostic for the approach to an ideal limit. However, the mode structure of the current driven RWM extends radially inwards, consistent with that in the pressure driven case for plasmas with q edge~2. This suggests that previously developed RWM feedback techniques together with the additional optimizations that enabled q edge~2 operation, can be applied to control of both current-driven and pressure-driven modes at high β N.« less

Coordination polymer gels with important environmental and biological applications.

PubMed

Jung, Jong Hwa; Lee, Ji Ha; Silverman, Julian R; John, George

2013-02-07

Coordination Polymer Gels (CPGs) constitute a subset of solid-like metal ion and bridging organic ligand structures (similar to metal-organic frameworks) that form multi-dimensional networks through a trapped solvent as a result of non-covalent interactions. While physical properties of these gels are similar to conventional high molecular weight organic polymer gels, coordination polymer gel systems are often fully reversible and can be assembled and disassembled in the presence of additional energy (heat, sonication, shaking) to give a solution of solvated gelators. Compared to gels resulting from purely organic self-assembled low molecular weight gelators, metal ions incorporated into the fibrilar networks spanning the bulk solvent can impart CPGs with added functionalities. The solid/liquid nature of the gels allows for species to migrate through the gel system and interact with metals, ligands, and the solvent. Chemosensing, catalysis, fluorescence, and drug-delivery applications are some of the many potential uses for these dynamic systems, taking advantage of the metal ion's coordination, the organic polydentate ligand's orientation and functionality, or a combination of these properties. By fine tuning these systems through metal ion and ligand selection and by directing self-assembly with external stimuli the rational synthesis of practical systems can be envisaged.

Syntheses and structural characterization of mercury (II) coordination polymers with neutral bidentate flexible pyrazole-based ligands

NASA Astrophysics Data System (ADS)

Lalegani, Arash; Khaledi Sardashti, Mohammad; Salavati, Hossein; Asadi, Amin; Gajda, Roman; Woźniak, Krzysztof

2016-03-01

Mercury(II) coordination compounds [Hg(μ-bbd)(μ-SCN)4]n(1) and [Hg(bpp)(SCN)2] (2) were synthesized by using the neutral flexible bidentate N-donor ligands 1,4-bis(3,5-dimethypyrazol-1-yl)butane (bbd) and 1,3-bis(3,5-dimethylpyrazolyl)propane (bpp), NCS- ligand and appropriate mercury(II) salts. Compound 1 forms a polymeric network with moieties which are connected by SCN groups and the mercury ions present as HgN3S2 trigonal bipyramides. The crystal structure of 2 is build of monomers and the mercury(II) ion adopts an HgN2S2 tetrahedral geometry. In the complex 1, each bbd acts as bridging ligand connecting Hg(μ-SCN)4 ions, while in the complex 2, the bpp ligand is coordinated to an mercury(II) ion in a cyclic-bidentate fashion forming an eight-membered metallocyclic ring. Moreover, in the tetrahedral structure of 2, the neutral molecules form a 1D chain structure through the C-H···N hydrogen bonds, whereas in 1 no hydrogen bonds are observed. Coordination compounds 1 and 2 have been characterized by infrared spectroscopy, elemental analyses and single-crystal X-ray diffraction.

Kinetic theory and Vlasov simulation of nonlinear ion-acoustic waves in multi-ion species plasmas.

PubMed

Chapman, T; Berger, R L; Brunner, S; Williams, E A

2013-05-10

The theory of damping and nonlinear frequency shifts from particles resonant with ion-acoustic waves (IAWs) is presented for multi-ion species plasma and compared to driven wave Vlasov simulations. Two distinct IAW modes may be supported in multi-ion species plasmas, broadly classified as fast and slow by their phase velocity relative to the constituent ion thermal velocities. In current fusion-relevant long pulse experiments, the ion to electron temperature ratio, T(i)/T(e), is expected to reach a level such that the least damped and thus more readily driven mode is the slow mode, with both linear and nonlinear properties that are shown to differ significantly from the fast mode. The lighter ion species of the slow mode is found to make no significant contribution to the IAW frequency shift despite typically being the dominant contributor to the Landau damping.

A method for computing ion energy distributions for multifrequency capacitive discharges

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

Wu, Alan C. F.; Lieberman, M. A.; Verboncoeur, J. P.

2007-03-01

The ion energy distribution (IED) at a surface is an important parameter for processing in multiple radio frequency driven capacitive discharges. An analytical model is developed for the IED in a low pressure discharge based on a linear transfer function that relates the time-varying sheath voltage to the time-varying ion energy response at the surface. This model is in good agreement with particle-in-cell simulations over a wide range of single, dual, and triple frequency driven capacitive discharge excitations.

Enhanced removal of azo dye using modified PAN nanofibrous membrane Fe complexes with adsorption/visible-driven photocatalysis bifunctional roles

NASA Astrophysics Data System (ADS)

Li, Fu; Dong, Yongchun; Kang, Weimin; Cheng, Bowen; Cui, Guixin

2017-05-01

A series of polyacrylonitrile (PAN) nanofibrous membrane Fe complexes as the Fenton heterogeneous catalysts were fabricated through surface modification with different ratio of hydrazine hydrate (HH) and hydroxylamine (HA) and subsequent coordination with Fe3+ ions for the synergistic removal of a typical azo dye, Reactive Red 195 (RR 195) via adsorption and visible-driven photocatalytic oxidation. Effect of molar ratio of HH and HA on surface structure characteristics of the resulting complexes were examined. Their adsorptive or photocatalytic activity was also compared by changing molar ratio of HH and HA. The results indicated that three PAN nanofibrous membrane Fe complexes prepared with simultaneous modification of HA and HH exhibited much higher adsorption and visible photocatalytic activities than the complex modified solely with HA or HH due to their distinctive surface structures containing more active sites. Their adsorption and visible photocatalytic kinetics of RR 195 followed pseudo-second-order model equation. Their high photocatalytic rate constant and large amount of dye adsorption were regarded as the main reasons for better dye removal efficiency and durability in cyclic reuse by means of the synergistic adsorption-photocatalysis process.

Perspectives of disproportionation driven superconductivity in strongly correlated 3d compounds.

PubMed

Moskvin, A S

2013-02-27

Disproportionation in 3d compounds can give rise to an unconventional electron-hole Bose liquid with a very rich phase diagram, from a Bose metal, to a charge ordering insulator and an inhomogeneous Bose-superfluid. Optimal conditions for disproportionation driven high-T(c) superconductivity are shown to be realized only for several Jahn-Teller d(n) configurations that permit the formation of well defined local composite bosons. These are the high-spin d(4), low-spin d(7), and d(9) configurations given the octahedral crystal field, and the d(1), high-spin d(6) configurations given the tetrahedral crystal field. The disproportionation reaction has a peculiar 'anti-Jahn-Teller' character lifting the bare orbital degeneracy. Superconductivity in the d(4) and d(6) systems at variance with d(1), d(7), and d(9) systems implies unavoidable coexistence of the spin-triplet composite bosons and the magnetic lattice. We argue that unconventional high-T(c) superconductivity, observed in quasi-2d cuprates with tetragonally distorted CuO(6) octahedra and iron-based layered pnictides/chalcogenides with tetrahedrally coordinated Fe(2+) ions presents a key argument to support the fact that the disproportionation scenario is at work in these compounds.

Characterisation of deuterium spectra from laser driven multi-species sources by employing differentially filtered image plate detectors in Thomson spectrometers.

PubMed

Alejo, A; Kar, S; Ahmed, H; Krygier, A G; Doria, D; Clarke, R; Fernandez, J; Freeman, R R; Fuchs, J; Green, A; Green, J S; Jung, D; Kleinschmidt, A; Lewis, C L S; Morrison, J T; Najmudin, Z; Nakamura, H; Nersisyan, G; Norreys, P; Notley, M; Oliver, M; Roth, M; Ruiz, J A; Vassura, L; Zepf, M; Borghesi, M

2014-09-01

A novel method for characterising the full spectrum of deuteron ions emitted by laser driven multi-species ion sources is discussed. The procedure is based on using differential filtering over the detector of a Thompson parabola ion spectrometer, which enables discrimination of deuterium ions from heavier ion species with the same charge-to-mass ratio (such as C(6+), O(8+), etc.). Commonly used Fuji Image plates were used as detectors in the spectrometer, whose absolute response to deuterium ions over a wide range of energies was calibrated by using slotted CR-39 nuclear track detectors. A typical deuterium ion spectrum diagnosed in a recent experimental campaign is presented, which was produced from a thin deuterated plastic foil target irradiated by a high power laser.

Characterisation of deuterium spectra from laser driven multi-species sources by employing differentially filtered image plate detectors in Thomson spectrometers

NASA Astrophysics Data System (ADS)

Alejo, A.; Kar, S.; Ahmed, H.; Krygier, A. G.; Doria, D.; Clarke, R.; Fernandez, J.; Freeman, R. R.; Fuchs, J.; Green, A.; Green, J. S.; Jung, D.; Kleinschmidt, A.; Lewis, C. L. S.; Morrison, J. T.; Najmudin, Z.; Nakamura, H.; Nersisyan, G.; Norreys, P.; Notley, M.; Oliver, M.; Roth, M.; Ruiz, J. A.; Vassura, L.; Zepf, M.; Borghesi, M.

2014-09-01

A novel method for characterising the full spectrum of deuteron ions emitted by laser driven multi-species ion sources is discussed. The procedure is based on using differential filtering over the detector of a Thompson parabola ion spectrometer, which enables discrimination of deuterium ions from heavier ion species with the same charge-to-mass ratio (such as C6 +, O8 +, etc.). Commonly used Fuji Image plates were used as detectors in the spectrometer, whose absolute response to deuterium ions over a wide range of energies was calibrated by using slotted CR-39 nuclear track detectors. A typical deuterium ion spectrum diagnosed in a recent experimental campaign is presented, which was produced from a thin deuterated plastic foil target irradiated by a high power laser.

Atomistic insights into deep eutectic electrolytes: the influence of urea on the electrolyte salt LiTFSI in view of electrochemical applications.

PubMed

Lesch, Volker; Heuer, Andreas; Rad, Babak R; Winter, Martin; Smiatek, Jens

2016-10-19

The influence of urea on the conducting salt lithium bis-(trifluoromethanesulfonyl)-imide (LiTFSI) in terms of lithium ion coordination numbers and lithium ion transport properties is studied via atomistic molecular dynamics simulations. Our results indicate that the presence of urea favors the formation of a deep eutectic electrolyte with pronounced ion conductivities which can be explained by a competition between urea and TFSI in occupying the first coordination shell around lithium ions. All simulation findings verify that high urea concentrations lead to a significant increase of ionic diffusivities and an occurrence of relatively high lithium transference numbers in good agreement with experimental results. The outcomes of our study point at the possible application of deep eutectic electrolytes as ion conducting materials in lithium ion batteries.

Crystal structure of metagenomic β-xylosidase/ α-l-arabinofuranosidase activated by calcium.

PubMed

Matsuzawa, Tomohiko; Kaneko, Satoshi; Kishine, Naomi; Fujimoto, Zui; Yaoi, Katsuro

2017-09-01

The crystal structure of metagenomic β-xylosidase/α-l-arabinofuranosidase CoXyl43, activated by calcium ions, was determined in its apo and complexed forms with xylotriose or l-arabinose in the presence and absence of calcium. The presence of calcium ions dramatically increases the kcat of CoXyl43 for p-nitrophenyl β-d-xylopyranoside and reduces the Michaelis constant for p-nitrophenyl α-l-arabinofuranoside. CoXyl43 consists of a single catalytic domain comprised of a five-bladed β-propeller. In the presence of calcium, a single calcium ion was observed at the centre of this catalytic domain, behind the catalytic pocket. In the absence of calcium, the calcium ion was replaced with one sodium ion and one water molecule, and the positions of these cations were shifted by 1.3 Å. The histidine-319 side chain, which coordinates to the 2-hydroxyl oxygen atom of the bound xylose molecule in the catalytic pocket, also coordinates to the calcium ion, but not to the sodium ion. The calcium-dependent increase in activity appears to be caused by the structural change in the catalytic pocket induced by the tightly bound calcium ion and coordinating water molecules, and by the protonation state of glutamic acid-268, the catalytic acid of the enzyme. Our findings further elucidate the complex relationship between metal ions and glycosidases. © The Authors 2017. Published by Oxford University Press on behalf of the Japanese Biochemical Society. All rights reserved.

Modulating the selectivity of affinity absorbents to multi-phosphopeptides by a competitive substitution strategy.

PubMed

Liu, Zheyi; Wang, Fangjun; Chen, Jin; Zhou, Ye; Zou, Hanfa

2016-08-26

Although many affinity adsorbents have been developed for phosphopeptides enrichment, high-specifically capturing the multi-phosphopeptides is still a big challenge. Here, we investigated the mechanism of phosphate ion coordination and substitution on affinity adsorbents surfaces and modulated the selectivity of affinity adsorbents to multi-phosphopeptides based on the different capability of mono- and multi-phosphopeptides in competitively substituting the pre-coordinated phosphate ions at strong acidic condition. We demonstrated both the species of pre-coordinated phosphate ions and the substituting conditions played crucial roles in modulating the enrichment selectivity to multi-phosphopeptides, and the pre-coordinated affinity materials with relative more surfaces positive charges exhibited better enrichment efficiency due to the cooperative effect of electrostatic interaction and competitive substitution. Finally, an enrichment selectivity of 85% to multi-phosphopeptides was feasibly achieved with 66% improvement in identification numbers for complex protein sample extracted from HepG2 cells. Data are available via ProteomeXchange with identifier PXD004252. Copyright © 2016 Elsevier B.V. All rights reserved.

Hydration of copper(II): new insights from density functional theory and the COSMO solvation model.

PubMed

Bryantsev, Vyacheslav S; Diallo, Mamadou S; van Duin, Adri C T; Goddard, William A

2008-09-25

The hydrated structure of the Cu(II) ion has been a subject of ongoing debate in the literature. In this article, we use density functional theory (B3LYP) and the COSMO continuum solvent model to characterize the structure and stability of [Cu(H2O)n](2+) clusters as a function of coordination number (4, 5, and 6) and cluster size (n = 4-18). We find that the most thermodynamically favored Cu(II) complexes in the gas phase have a very open four-coordinate structure. They are formed from a stable square-planar [Cu(H2O)8](2+) core stabilized by an unpaired electron in the Cu(II) ion d(x(2)-y(2)) orbital. This is consistent with cluster geometries suggested by recent mass-spectrometric experiments. In the aqueous phase, we find that the more compact five-coordinate square-pyramidal geometry is more stable than either the four-coordinate or six-coordinate clusters in agreement with recent combined EXAFS and XANES studies of aqueous solutions of Cu(II). However, a small energetic difference (approximately 1.4 kcal/mol) between the five- and six-coordinate models with two full hydration shells around the metal ion suggests that both forms may coexist in solution.

Self-sorting of dynamic metallosupramolecular libraries (DMLs) via metal-driven selection.

PubMed

Kocsis, Istvan; Dumitrescu, Dan; Legrand, Yves-Marie; van der Lee, Arie; Grosu, Ion; Barboiu, Mihail

2014-03-11

"Metal-driven" selection between finite mononuclear and polymeric metallosupramolecular species can be quantitatively achieved in solution and in a crystalline state via coupled coordination/stacking interactional algorithms within dynamic metallosupramolecular libraries - DMLs.

H(+)/solute-induced intracellular acidification leads to selective activation of apical Na(+)/H(+) exchange in human intestinal epithelial cells.

PubMed

Thwaites, D T; Ford, D; Glanville, M; Simmons, N L

1999-09-01

The intestinal absorption of many nutrients and drug molecules is mediated by ion-driven transport mechanisms in the intestinal enterocyte plasma membrane. Clearly, the establishment and maintenance of the driving forces - transepithelial ion gradients - are vital for maximum nutrient absorption. The purpose of this study was to determine the nature of intracellular pH (pH(i)) regulation in response to H(+)-coupled transport at the apical membrane of human intestinal epithelial Caco-2 cells. Using isoform-specific primers, mRNA transcripts of the Na(+)/H(+) exchangers NHE1, NHE2, and NHE3 were detected by RT-PCR, and identities were confirmed by sequencing. The functional profile of Na(+)/H(+) exchange was determined by a combination of pH(i), (22)Na(+) influx, and EIPA inhibition experiments. Functional NHE1 and NHE3 activities were identified at the basolateral and apical membranes, respectively. H(+)/solute-induced acidification (using glycylsarcosine or beta-alanine) led to Na(+)-dependent, EIPA-inhibitable pH(i) recovery or EIPA-inhibitable (22)Na(+) influx at the apical membrane only. Selective activation of apical (but not basolateral) Na(+)/H(+) exchange by H(+)/solute cotransport demonstrates that coordinated activity of H(+)/solute symport with apical Na(+)/H(+) exchange optimizes the efficient absorption of nutrients and Na(+), while maintaining pH(i) and the ion gradients involved in driving transport.

Solvate Structures and Computational/Spectroscopic Characterization of LiPF6 Electrolytes

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

Han, Sang D.; Yun, Sung-Hyun; Borodin, Oleg

2015-04-23

Raman spectroscopy is a powerful method for identifying ion-ion interactions, but only if the vibrational band signature for the anion coordination modes can be accurately deciphered. The present study characterizes the PF6- anion P-F Raman symmetric stretching vibrational band for evaluating the PF6-...Li+ cation interactions within LiPF6 crystalline solvates to create a characterization tool for liquid electrolytes. To facilitate this, the crystal structures for two new solvates—(G3)1:LiPF6 and (DEC)2:LiPF6 with triglyme and diethyl carbonate, respectively—are reported. The information obtained from this analysis provides key guidance about the ionic association information which may be obtained from a Raman spectroscopic evaluation ofmore » electrolytes containing the LiPF6 salt and aprotic solvents. Of particular note is the overlap of the Raman bands for both solvent-separated ion pair (SSIP) and contact ion pair (CIP) coordination in which the PF6- anions are uncoordinated or coordinated to a single Li+ cation, respectively.« less

Organic active materials for batteries

DOEpatents

Abouimrane, Ali; Weng, Wei; Amine, Khalil

2016-08-16

A rechargeable battery includes a compound having at least two active sites, R.sup.1 and R.sup.2; wherein the at least two active sites are interconnected by one or more conjugated moieties; each active site is coordinated to one or more metal ions M.sup.a+ or each active site is configured to coordinate to one or more metal ions; and "a" is 1, 2, or 3.

Origin of Blue-Green Emission in α-Zn2P2O7 and Local Structure of Ln3+ Ion in α-Zn2P2O7:Ln3+ (Ln = Sm, Eu): Time-Resolved Photoluminescence, EXAFS, and DFT Measurements.

PubMed

Gupta, Santosh Kumar; Ghosh, Partha Sarathi; Yadav, Ashok Kumar; Jha, Shambhu Nath; Bhattacharyya, Dibyendu; Kadam, Ramakant Mahadeo

2017-01-03

Considering the fact that pyrophosphate-based hosts are in high demand for making highly efficient luminescence materials, we doped two visible lanthanide ions, viz. Sm 3+ and Eu 3+ , in Zn 2 P 2 O 7 . Interestingly, it was oberved that pure Zn 2 P 2 O 7 displayed blue-green dual emission on irradiation with ultraviolet light. Emission and lifetime spectroscopy shows the presence of defects in pyrophosphate samples which are responsible for such emission. DFT calculations clearly pinpointed that the electronic transitions between defect states located at just below the conduction band minimum (arises due to V O 1+ and V O 2+ defects) and valence band maximum, as well as impurity states situated in the band gap, can lead to dual emission in the blue-green region, as is also indicated by emission and lifetime spectra. X-ray absorption near edge spectroscopy (XANES) shows the stabilization of europium as well as samarium ion in the +3 oxidation state in α-Zn 2 P 2 O 7 . The fact that α-Zn 2 P 2 O 7 has two different coordination numbers for zinc ions, i.e. five- and six-coordinate, the study of dopant ion distribution in this particular matrix will be an important step in realizing a highly efficient europium- and samarium-based red-emitting phosphor. Time resolved photoluminescence (TRPL) shows that both of these ions are heterogeneously distributed between five- and six-coordinated Zn 2+ sites and it is the six-coordinated Zn 2+ site which is the most favorable for lanthanide ion doping. Extended X-ray absorption fine structure (EXAFS) measurements also suggested that a six-coordinated zinc ion is the preferred site occupied by trivalent lanthanide ions, which is in complete agreement with TRPL results. It was observed that there is almost complete transfer of photon energy from Zn 2 P 2 O 7 to Eu 3+ , whereas this transfer is inefficient and almost incomplete in case of Sm 3+ , which is indeed important information for the realization of pyrophosphate-based tunable phosphors.

Towards highest peak intensities for ultra-short MeV-range ion bunches

NASA Astrophysics Data System (ADS)

Busold, Simon; Schumacher, Dennis; Brabetz, Christian; Jahn, Diana; Kroll, Florian; Deppert, Oliver; Schramm, Ulrich; Cowan, Thomas E.; Blažević, Abel; Bagnoud, Vincent; Roth, Markus

2015-07-01

A laser-driven, multi-MeV-range ion beamline has been installed at the GSI Helmholtz center for heavy ion research. The high-power laser PHELIX drives the very short (picosecond) ion acceleration on μm scale, with energies ranging up to 28.4 MeV for protons in a continuous spectrum. The necessary beam shaping behind the source is accomplished by applying magnetic ion lenses like solenoids and quadrupoles and a radiofrequency cavity. Based on the unique beam properties from the laser-driven source, high-current single bunches could be produced and characterized in a recent experiment: At a central energy of 7.8 MeV, up to 5 × 108 protons could be re-focused in time to a FWHM bunch length of τ = (462 ± 40) ps via phase focusing. The bunches show a moderate energy spread between 10% and 15% (ΔE/E0 at FWHM) and are available at 6 m distance to the source und thus separated from the harsh laser-matter interaction environment. These successful experiments represent the basis for developing novel laser-driven ion beamlines and accessing highest peak intensities for ultra-short MeV-range ion bunches.

Towards highest peak intensities for ultra-short MeV-range ion bunches

PubMed Central

Busold, Simon; Schumacher, Dennis; Brabetz, Christian; Jahn, Diana; Kroll, Florian; Deppert, Oliver; Schramm, Ulrich; Cowan, Thomas E.; Blažević, Abel; Bagnoud, Vincent; Roth, Markus

2015-01-01

A laser-driven, multi-MeV-range ion beamline has been installed at the GSI Helmholtz center for heavy ion research. The high-power laser PHELIX drives the very short (picosecond) ion acceleration on μm scale, with energies ranging up to 28.4 MeV for protons in a continuous spectrum. The necessary beam shaping behind the source is accomplished by applying magnetic ion lenses like solenoids and quadrupoles and a radiofrequency cavity. Based on the unique beam properties from the laser-driven source, high-current single bunches could be produced and characterized in a recent experiment: At a central energy of 7.8 MeV, up to 5 × 108 protons could be re-focused in time to a FWHM bunch length of τ = (462 ± 40) ps via phase focusing. The bunches show a moderate energy spread between 10% and 15% (ΔE/E0 at FWHM) and are available at 6 m distance to the source und thus separated from the harsh laser-matter interaction environment. These successful experiments represent the basis for developing novel laser-driven ion beamlines and accessing highest peak intensities for ultra-short MeV-range ion bunches. PMID:26212024

Stochastic Acceleration of Ions Driven by Pc1 Wave Packets

NASA Technical Reports Server (NTRS)

Khazanov, G. V.; Sibeck, D. G.; Tel'nikhin, A. A.; Kronberg, T. K.

2015-01-01

The stochastic motion of protons and He(sup +) ions driven by Pc1 wave packets is studied in the context of resonant particle heating. Resonant ion cyclotron heating typically occurs when wave powers exceed 10(exp -4) nT sq/Hz. Gyroresonance breaks the first adiabatic invariant and energizes keV ions. Cherenkov resonances with the electrostatic component of wave packets can also accelerate ions. The main effect of this interaction is to accelerate thermal protons to the local Alfven speed. The dependencies of observable quantities on the wave power and plasma parameters are determined, and estimates for the heating extent and rate of particle heating in these wave-particle interactions are shown to be in reasonable agreement with known empirical data.

Non-covalent and coordination interactions in Cu(II) systems with uridine, uridine 5'-monophosphate and triamine or tetramine as biogenic amine analogues in aqueous solutions.

PubMed

Łomozik, Lechosław; Jastrzab, Renata

2003-10-01

Reactions of metallation and non-covalent interactions have been studied in ternary systems of Cu(II) ions with uridine, uridine 5'-monophosphate and diamines or triamines. It has been found that in metal-free systems the reaction centres of the nucleoside with the polyamine are the donor nitrogen atoms N(3) and protonated -NH(x) groups of the amines. In comparison to systems with adenosine or cytidine, the pH range of complex formation is shifted towards higher values. It is a consequence of significantly higher basicity of uridine and in agreement with the ion-ion, ion-dipole interaction model assumed. Formation of molecular complexes of uridine 5'-monophosphate with polyamines at a low pH is the result of activity of the phosphate group which plays the role of a negatively charged reaction site. Non-covalent interactions interfere in processes of bioligand metallation. Centres of weak interactions are simultaneously binding sites of metal ions. In protonated Cu(Urd)(PA)H(x) complexes, coordination has been found to involve the N(3) atom from the nucleoside and two donor nitrogen atoms from the polyamine (PA). In the heteroligand species Cu(Urd)(PA), despite deprotonation of all amine groups, one of these groups is located outside the inner coordination sphere. In complexes with uridine-5'-monophosphate, the phosphate group is active in metallation. Moreover, in certain coordination compounds this group is engaged in non-covalent interactions with PA molecules, despite binding Cu ions, as has been shown on the basis of equilibrium and spectral studies.

Ferromagnetism in LaCo O3

NASA Astrophysics Data System (ADS)

Yan, J.-Q.; Zhou, J.-S.; Goodenough, J. B.

2004-07-01

A systematic investigation of the low-temperature magnetic properties of LaCoO3 has demonstrated a ferromagnetism with Tc≈85K from surface cobalt atoms. The experimental investigation involved comparison of the magnetic susceptibility of (1) a single crystal, (2) a powder ground from the same crystal, and (3) a cold-pressed pellet from the ground powder that was unannealed and annealed at 400°C followed by a later anneal at 1000°C . The low-temperature magnetic susceptibility was found to have three contributions: a Curie-Weiss paramagnetism, a thermally driven spin-state transition, and a surface-related ferromagnetism with Tc≈85K . The ferromagnetic component has a remanence and coercivity at 5K that increases dramatically with increasing surface/volume ratio of the different samples. The presence of the surface ferromagnetism explains the discrepancies of the low-temperature magnetic susceptibility reported by different groups. An anion coordination at surface Co(III) ions that differs from that of the bulk cobalt is shown to be capable of stabilizing higher spin states. A Tc≈85K is argued to be too low for ferromagnetic coupling by oxidized clusters, and possible mechanisms for a ferromagnetic coupling between higher-spin Co(III) ions are discussed.

Facile construction of terpridine-based metallo-polymers in hydrogels, crystals and solutions directed by metal ions.

PubMed

Li, Yajuan; Guo, Jiangbo; Dai, Bo; Geng, Lijun; Shen, Fengjuan; Zhang, Yajun; Yu, Xudong

2018-07-01

Driven by tunable metal-ligand interactions, a polydentate ligand TC containing terpyridine and carboxylic acid units was developed to construct metallo-polymers that showed multiple aggregation modes with controlled macroscopic properties. In the presence of different kind of Zn 2+ ions or NaOH, TC could form metallo-polymers via π-π stacking and metal-ligand interaction that further trapped water molecules, resulting in hydrogels and crystals. Moreover, these TC/Zn 2+ hydrogels could transform to soluble and fluorescent aggregates in the presence of NaOH due to the formation of binuclear metallo-polymers with enhanced ICT emission. The metal-ligand interactions tuned by different metal salts in gels, crystals, and sols were also studied and illustrated in detail, it was also proved that water was an essential linker for constructing Na + -based metallo-polymers from the TC/NaOH crystal data. This work demonstrated the engineered coordination pathways in generating controllable hydrogels and metallo-polymers for the first time, which led to novel approach for facilely constructing a number of hydrogels with tailorable macroscopic properties. Copyright © 2018 Elsevier Inc. All rights reserved.

Coulomb-driven energy boost of heavy ions for laser-plasma acceleration.

PubMed

Braenzel, J; Andreev, A A; Platonov, K; Klingsporn, M; Ehrentraut, L; Sandner, W; Schnürer, M

2015-03-27

An unprecedented increase of kinetic energy of laser accelerated heavy ions is demonstrated. Ultrathin gold foils have been irradiated by an ultrashort laser pulse at a peak intensity of 8×10^{19}  W/  cm^{2}. Highly charged gold ions with kinetic energies up to >200  MeV and a bandwidth limited energy distribution have been reached by using 1.3 J laser energy on target. 1D and 2D particle in cell simulations show how a spatial dependence on the ion's ionization leads to an enhancement of the accelerating electrical field. Our theoretical model considers a spatial distribution of the ionization inside the thin target, leading to a field enhancement for the heavy ions by Coulomb explosion. It is capable of explaining the energy boost of highly charged ions, enabling a higher efficiency for the laser-driven heavy ion acceleration.

Enhanced electron/fuel-ion equilibration through impurity ions: Studies applicable to NIF and Omega

NASA Astrophysics Data System (ADS)

Petrasso, R. D.; Sio, H.; Kabadi, N.; Lahmann, B.; Simpson, R.; Parker, C.; Frenje, J.; Gatu Johnson, M.; Li, C. K.; Seguin, F. H.; Rinderknecht, H.; Casey, D.; Grabowski, P.; Graziani, F.; Taitano, W.; Le, A.; Chacon, L.; Hoffman, N.; Kagan, G.; Simakov, A.; Zylstra, A.; Rosenberg, M.; Betti, R.; Srinivasan, B.; Mancini, R.

2017-10-01

In shock-driven exploding-pushers, a platform used extensively to study multi-species and kinetic effects, electrons and fuel ions are far out of equilibrium, as reflected by very different temperatures. However, impurity ions, even in small quantities, can couple effectively to the electrons, because of a Z2 dependence, and in turn, impurity ions can then strongly couple to the fuel ions. Through this mechanism, electrons and fuel-ions can equilibrate much faster than they otherwise would. This is a quantitative issue, depending upon the amount and Z of the impurity. For NIF and Omega, we consider the role of this process. Coupled non-linear equations, reflecting the temperatures of the three species, are solved for a range of conditions. Consideration is also given to ablatively driven implosions, since impurities can similarly affect the equilibration. This work was supported in part by DOE/NNSA DE-NA0002949 and DE-NA0002726.

Sodium recognition by the Na+/Ca2+ exchanger in the outward-facing conformation

PubMed Central

Marinelli, Fabrizio; Almagor, Lior; Hiller, Reuben; Giladi, Moshe; Khananshvili, Daniel; Faraldo-Gómez, José D.

2014-01-01

Na+/Ca2+ exchangers (NCXs) are ubiquitous membrane transporters with a key role in Ca2+ homeostasis and signaling. NCXs mediate the bidirectional translocation of either Na+ or Ca2+, and thus can catalyze uphill Ca2+ transport driven by a Na+ gradient, or vice versa. In a major breakthrough, a prokaryotic NCX homolog (NCX_Mj) was recently isolated and its crystal structure determined at atomic resolution. The structure revealed an intriguing architecture consisting of two inverted-topology repeats, each comprising five transmembrane helices. These repeats adopt asymmetric conformations, yielding an outward-facing occluded state. The crystal structure also revealed four putative ion-binding sites, but the occupancy and specificity thereof could not be conclusively established. Here, we use molecular-dynamics simulations and free-energy calculations to identify the ion configuration that best corresponds to the crystallographic data and that is also thermodynamically optimal. In this most probable configuration, three Na+ ions occupy the so-called Sext, SCa, and Sint sites, whereas the Smid site is occupied by one water molecule and one H+, which protonates an adjacent aspartate side chain (D240). Experimental measurements of Na+/Ca2+ and Ca2+/Ca2+ exchange by wild-type and mutagenized NCX_Mj confirm that transport of both Na+ and Ca2+ requires protonation of D240, and that this side chain does not coordinate either ion at Smid. These results imply that the ion exchange stoichiometry of NCX_Mj is 3:1 and that translocation of Na+ across the membrane is electrogenic, whereas transport of Ca2+ is not. Altogether, these findings provide the basis for further experimental and computational studies of the conformational mechanism of this exchanger. PMID:25468964

Sodium recognition by the Na+/Ca2+ exchanger in the outward-facing conformation.

PubMed

Marinelli, Fabrizio; Almagor, Lior; Hiller, Reuben; Giladi, Moshe; Khananshvili, Daniel; Faraldo-Gómez, José D

2014-12-16

Na(+)/Ca(2+) exchangers (NCXs) are ubiquitous membrane transporters with a key role in Ca(2+) homeostasis and signaling. NCXs mediate the bidirectional translocation of either Na(+) or Ca(2+), and thus can catalyze uphill Ca(2+) transport driven by a Na(+) gradient, or vice versa. In a major breakthrough, a prokaryotic NCX homolog (NCX_Mj) was recently isolated and its crystal structure determined at atomic resolution. The structure revealed an intriguing architecture consisting of two inverted-topology repeats, each comprising five transmembrane helices. These repeats adopt asymmetric conformations, yielding an outward-facing occluded state. The crystal structure also revealed four putative ion-binding sites, but the occupancy and specificity thereof could not be conclusively established. Here, we use molecular-dynamics simulations and free-energy calculations to identify the ion configuration that best corresponds to the crystallographic data and that is also thermodynamically optimal. In this most probable configuration, three Na(+) ions occupy the so-called Sext, SCa, and Sint sites, whereas the Smid site is occupied by one water molecule and one H(+), which protonates an adjacent aspartate side chain (D240). Experimental measurements of Na(+)/Ca(2+) and Ca(2+)/Ca(2+) exchange by wild-type and mutagenized NCX_Mj confirm that transport of both Na(+) and Ca(2+) requires protonation of D240, and that this side chain does not coordinate either ion at Smid. These results imply that the ion exchange stoichiometry of NCX_Mj is 3:1 and that translocation of Na(+) across the membrane is electrogenic, whereas transport of Ca(2+) is not. Altogether, these findings provide the basis for further experimental and computational studies of the conformational mechanism of this exchanger.

Asymmetric Preorganization of Inverted Pair Residues in the Sodium-Calcium Exchanger

PubMed Central

Giladi, Moshe; Almagor, Lior; van Dijk, Liat; Hiller, Reuben; Man, Petr; Forest, Eric; Khananshvili, Daniel

2016-01-01

In analogy with many other proteins, Na+/Ca2+ exchangers (NCX) adapt an inverted twofold symmetry of repeated structural elements, while exhibiting a functional asymmetry by stabilizing an outward-facing conformation. Here, structure-based mutant analyses of the Methanococcus jannaschii Na+/Ca2+ exchanger (NCX_Mj) were performed in conjunction with HDX-MS (hydrogen/deuterium exchange mass spectrometry) to identify the structure-dynamic determinants of functional asymmetry. HDX-MS identified hallmark differences in backbone dynamics at ion-coordinating residues of apo-NCX_Mj, whereas Na+or Ca2+ binding to the respective sites induced relatively small, but specific, changes in backbone dynamics. Mutant analysis identified ion-coordinating residues affecting the catalytic capacity (kcat/Km), but not the stability of the outward-facing conformation. In contrast, distinct “noncatalytic” residues (adjacent to the ion-coordinating residues) control the stability of the outward-facing conformation, but not the catalytic capacity. The helix-breaking signature sequences (GTSLPE) on the α1 and α2 repeats (at the ion-binding core) differ in their folding/unfolding dynamics, while providing asymmetric contributions to transport activities. The present data strongly support the idea that asymmetric preorganization of the ligand-free ion-pocket predefines catalytic reorganization of ion-bound residues, where secondary interactions with adjacent residues couple the alternating access. These findings provide a structure-dynamic basis for ion-coupled alternating access in NCX and similar proteins. PMID:26876271

Interaction of NaOH solutions with silica surfaces

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

Rimsza, Jessica M.; Jones, Reese E.; Criscenti, Louise J.

Sodium adsorption on silica surfaces depends on the solution counter-ion. Here, we use NaOH solutions to investigate basic environments. Sodium adsorption on hydroxylated silica surfaces from NaOH solutions were investigated through molecular dynamics with a dissociative force field, allowing for the development of secondary molecular species. Furthermore, across the NaOH concentrations (0.01 M – 1.0 M), ~50% of the Na + ions were concentrated in the surface region, developing silica surface charges between –0.01 C/m 2 (0.01 M NaOH) and –0.76 C/m 2 (1.0 M NaOH) due to surface site deprotonation. Five inner-sphere adsorption complexes were identified, including monodentate, bidentate,more » and tridentate configurations and two additional structures, with Na + ions coordinated by bridging oxygen and hydroxyl groups or water molecules. Coordination of Na + ions by bridging oxygen atoms indicates partial or complete incorporation of Na + ions into the silica surface. Residence time analysis identified that Na + ions coordinated by bridging oxygen atoms stayed adsorbed onto the surface four times longer than the mono/bi/tridentate species, indicating formation of relatively stable and persistent Na + ion adsorption structures. Such inner-sphere complexes form only at NaOH concentrations of > 0.5 M. Na + adsorption and lifetimes have implications for the stability of silica surfaces.« less

Interaction of NaOH solutions with silica surfaces

DOE PAGES

Rimsza, Jessica M.; Jones, Reese E.; Criscenti, Louise J.

2018-01-16

Sodium adsorption on silica surfaces depends on the solution counter-ion. Here, we use NaOH solutions to investigate basic environments. Sodium adsorption on hydroxylated silica surfaces from NaOH solutions were investigated through molecular dynamics with a dissociative force field, allowing for the development of secondary molecular species. Furthermore, across the NaOH concentrations (0.01 M – 1.0 M), ~50% of the Na + ions were concentrated in the surface region, developing silica surface charges between –0.01 C/m 2 (0.01 M NaOH) and –0.76 C/m 2 (1.0 M NaOH) due to surface site deprotonation. Five inner-sphere adsorption complexes were identified, including monodentate, bidentate,more » and tridentate configurations and two additional structures, with Na + ions coordinated by bridging oxygen and hydroxyl groups or water molecules. Coordination of Na + ions by bridging oxygen atoms indicates partial or complete incorporation of Na + ions into the silica surface. Residence time analysis identified that Na + ions coordinated by bridging oxygen atoms stayed adsorbed onto the surface four times longer than the mono/bi/tridentate species, indicating formation of relatively stable and persistent Na + ion adsorption structures. Such inner-sphere complexes form only at NaOH concentrations of > 0.5 M. Na + adsorption and lifetimes have implications for the stability of silica surfaces.« less

3D chiral and 2D achiral cobalt(ii) compounds constructed from a 4-(benzimidazole-1-yl)benzoic ligand exhibiting field-induced single-ion-magnet-type slow magnetic relaxation.

PubMed

Wang, Yu-Ling; Chen, Lin; Liu, Cai-Ming; Du, Zi-Yi; Chen, Li-Li; Liu, Qing-Yan

2016-05-04

Organizing magnetically isolated 3d transition metal ions, which behave as single-ion magnet (SIM) units, in a coordination network is a promising approach to design novel single-molecule magnets (SMMs). Herein 3D chiral and 2D achiral cobalt(ii) coordination compounds based on single metal nodes with a 4-(benzimidazole-1-yl)benzoic acid (Hbmzbc) ligand, namely, [Co(bmzbc)2(1,2-etdio)]n () (1,2-etdio = 1,2-ethanediol) and [Co(bmzbc)2(Hbmzbc)]n (), have been synthesized and structurally characterized. The 3D chiral structure with 2-fold interpenetrating qtz topological nets consisting of totally achiral components was obtained via spontaneous resolution, while the achiral structure is a 2D (4,4) net. In both structures, individual cobalt(ii) ions are spatially well separated by the long organic ligands in the well-defined networks. Magnetic measurements on and showed field-induced slow magnetic relaxation resulting from single-ion anisotropy of the individual Co(ii) ions. Analysis of the dynamic ac susceptibilities with the Arrhenius law afforded an anisotropy energy barrier of 16.8(3) and 31.3(2) K under a 2 kOe static magnetic field for and , respectively. The distinct coordination environments of the Co(ii) ions in and lead to the different anisotropic energy barriers.

Two-fluid flowing equilibria of spherical torus sustained by coaxial helicity injection

NASA Astrophysics Data System (ADS)

Kanki, Takashi; Steinhauer, Loren; Nagata, Masayoshi

2007-11-01

Two-dimensional equilibria in helicity-driven systems using two-fluid model were previously computed, showing the existence of an ultra-low-q spherical torus (ST) configuration with diamagnetism and higher beta. However, this computation assumed purely toroidal ion flow and uniform density. The purpose of the present study is to apply the two-fluid model to the two-dimensional equilibria of helicity-driven ST with non-uniform density and both toroidal and poloidal flows for each species by means of the nearby-fluids procedure, and to explore their properties. We focus our attention on the equilibria relevant to the HIST device, which are characterized by either driven or decaying λ profiles. The equilibrium for the driven λ profile has a diamagnetic toroidal field, high-β (βt = 32%), and centrally broad density. By contrast, the decaying equilibrium has a paramagnetic toroidal field, low-β (βt = 10%), and centrally peaked density with a steep gradient in the outer edge region. In the driven case, the toroidal ion and electron flows are in the same direction, and two-fluid effects are less important since the ExB drift is dominant. In the decaying case, the toroidal ion and electron flows are opposite in the outer edge region, and two-fluid effects are significant locally in the edge due to the ion diamagnetic drift.

Ion Thermal Decoupling and Species Separation in Shock-Driven Implosions

DOE PAGES

Rinderknecht, Hans G.; Rosenberg, M. J.; Li, C. K.; ...

2015-01-14

Here, anomalous reduction of the fusion yields by 50% and anomalous scaling of the burn-averaged ion temperatures with the ion-species fraction has been observed for the first time in D 3He-filled shock-driven inertial confinement fusion implosions. Two ion kinetic mechanisms are used to explain the anomalous observations: thermal decoupling of the D and 3He populations and diffusive species separation. The observed insensitivity of ion temperature to a varying deuterium fraction is shown to be a signature of ion thermal decoupling in shock-heated plasmas. The burn-averaged deuterium fraction calculated from the experimental data demonstrates a reduction in the average core deuteriummore » density, as predicted by simulations that use a diffusion model. Accounting for each of these effects in simulations reproduces the observed yield trends.« less

Ion acceleration by laser hole-boring into plasmas

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

Pogorelsky, I. V.; Dover, N. P.; Babzien, M.

By experiment and simulations, we study the interaction of an intense CO{sub 2} laser pulse with slightly overcritical plasmas of fully ionized helium gas. Transverse optical probing is used to show a recession of the front plasma surface with an initial velocity >10{sup 6} m/s driven by hole-boring by the laser pulse and the resulting radiation pressure driven electrostatic shocks. The collisionless shock propagates through the plasma, dissipates into an ion-acoustic solitary wave, and eventually becomes collisional as it slows further. These observations are supported by PIC simulations which prove the conclusion that monoenergetic protons observed in our earlier reportedmore » experiment with a hydrogen jet result from ion trapping and reflection from a shock wave driven through the plasma.« less

Cadmium-1,4-cyclohexanedicarboxylato coordination polymers bearing different di-alkyl-2,2'-bipyridines: syntheses, crystal structures and photoluminescence studies.

PubMed

Rosales-Vázquez, Luis D; Sánchez-Mendieta, Víctor; Dorazco-González, Alejandro; Martínez-Otero, Diego; García-Orozco, Iván; Morales-Luckie, Raúl A; Jaramillo-Garcia, Jonathan; Téllez-López, Antonio

2017-09-26

Four coordination polymers have been synthesized using self-assembly solution reactions under ambient conditions, reacting Cd(ii) ions with 1,4-cyclohexanedicarboxylic acid in the presence of different 2,2'-bipyridine co-ligands: {[Cd(H 2 O)(e,a-cis-1,4-chdc)(2,2'-bpy)]·H 2 O} n (1); [Cd 2 (H 2 O) 2 (e,a-cis-1,4-chdc) 2 (4,4'-dmb) 2 ] n (2); {[Cd(e,a-cis-1,4-chdc)(5,5'-dmb)]·H 2 O·CH 3 OH} n (3) and {[Cd(e,e-trans-1,4-chdc)(4,4'-dtbb)]·CH 3 OH} n (4), where 1,4-chdc = 1,4-cyclohexanedicarboxylato, 2,2'-bpy = 2,2'-bipyridine, 4,4'-dmb = 4,4'-dimethyl-2,2'-bipyridine, 5,5'-dmb = 5,5'-dimethyl-2,2'-bipyridine and 4,4'-dtbb = 4,4'-di-tert-butyl-2,2'-bipyridine. Crystallographic studies show that compound 1 has a 1D structure propagating along the crystallographic b-axis; the Cd ion in 1 is six-coordinated with a distorted-octahedral coordination sphere. Compound 2 has two crystallographic different Cd ions and both are six-coordinated with a distorted-octahedral coordination sphere. Compound 3 exhibits a seven-coordinated Cd ion having a distinctive distorted-monocapped trigonal prismatic geometry. In compound 4, the Cd ion is also seven-coordinated in a distorted monocapped octahedral geometry. Compounds 2, 3 and 4 possess rhombic-shaped dinuclear units (Cd 2 O 2 ) as nodes to generate larger cycles made up of four dinuclear units, a Cd 4 motif, bridged by four 1,4-chdc ligands, accomplishing, thus, 2D structures. Remarkably, in compound 4 the 1,4-chdc ligand conformation changes to the equatorial, equatorial trans, unlike the other compounds where the bridging ligand conformation is the more typical equatorial, axial cis. The solid state luminescence properties of 1-4 were investigated; polymers 3 and 4 exhibited a strong blue emission (λ em = 410-414 nm) compared to 1 and 2; structure-related photoluminescence is attributed to the degree of hydration of the compounds. Furthermore, Cd-polymer 3 suspended in acetone allows the fluorescence selective sensing of acetonitrile over common organic solvents such as alcohols and DMF, based on turn-on fluorescence intensity with a limit of 53 μmol L -1 .

Direct and Quantitative Characterization of Dynamic Ligand Exchange between Coordination-Driven Self-Assembled Supramolecular Polygons

PubMed Central

Zheng, Yao-Rong; Stang, Peter J.

2009-01-01

The direct observation of dynamic ligand exchange beween Pt-N coordination-driven self-assembled supramolecular polygons (triangles and rectangles) has been achieved using stable isotope labeling (1H/2D) of the pyridyl donors and electrospray ionization mass spectrometry (ESI-MS) together with NMR spectroscopy. Both the thermodynamic and kinetic aspects of such exchange processes have been established based on quantitative mass spectral results. Further investigation showed that the exchange is highly dependent on experimental conditions such as temperature, solvent, and the counter anions. PMID:19243144

Direct and quantitative characterization of dynamic ligand exchange between coordination-driven self-assembled supramolecular polygons.

PubMed

Zheng, Yao-Rong; Stang, Peter J

2009-03-18

The direct observation of dynamic ligand exchange between Pt-N coordination-driven self-assembled supramolecular polygons (triangles and rectangles) has been achieved using stable (1)H/(2)D isotope labeling of the pyridyl donors and electrospray ionization mass spectrometry combined with NMR spectroscopy. Both the thermodynamic and kinetic aspects of such exchange processes have been established on the basis of quantitative mass spectral results. Further investigation has shown that the exchange is highly dependent on experimental conditions such as temperature, solvent, and the counteranions.

Following the movement of Cu ions in a SSZ-13 zeolite during dehydration, reduction and adsorption: a combined in situ TP-XRD, XANES/DRIFTS study

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

Kwak, Ja Hun; Varga, Tamas; Peden, Charles HF

2014-05-05

Cu-SSZ-13 has been shown to possess high activity and superior N2 formation selectivity in the selective catalytic reduction of NOx under oxygen rich conditions. Here, a combination of synchrotron-based (XRD and XANES) and vibrational (DRIFTS) spectroscopy tools have been used to follow the changes in the location and coordination environment of copper ions in a Cu-SSZ-13 zeolite during calcinations, reduction with CO, and adsorption of CO and H2O. XANES spectra collected during these procedures provides critical information not only on the variation in the oxidation state of the copper species in the zeolite structure, but also on the changes inmore » the coordination environment around these ions as they interact with the framework, and with different adsorbates (H2O and CO). Time-resolved XRD data indicate the movement of copper ions and the consequent variation of the unit cell parameters during dehydration. DRIFT spectra provide information about the adsorbed species present in the zeolite, as well as the oxidation states of and coordination environment around the copper ions. A careful analysis of the asymmetric T-O-T vibrations of the CHA framework perturbed by copper ions in different coordination environments proved to be especially informative. The results of this study will aid the identification of the location, coordination and oxidation states of copper ions obtained during in operando catalytic studies. Financial support was provided by the US Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Program. Part of this work (sample preparation) was performed in the Environmental Molecular Sciences Laboratory (EMSL) at Pacific Northwest National Laboratory (PNNL). The EMSL is a national scientific user facility supported by the US DOE, Office of Biological and Environmental Research. PNNL is a multi-program national laboratory operated for the US DOE by Battelle. All of the spectroscopy work reported here was carried out at the National Synchrotron Light Source (NSLS) at Brookhaven National Laboratory (BNL). NSLS is a national scientific user facility supported by the US DOE.« less

A coordination chemistry study of hydrated and solvated cationic vanadium ions in oxidation states +III, +IV, and +V in solution and solid state

PubMed Central

Krakowiak, Joanna; Lundberg, Daniel

2012-01-01

The coordination chemistry of hydrated and solvated vanadium(III), oxovanadium(IV), and dioxovanadium(V) ions in the oxygen donor solvents water, dimethylsulfoxide (dmso) and N,N′-dimethylpropyleneurea (dmpu) has been studied in solution by EXAFS and large angle X-ray scattering (LAXS) and in solid state by single crystal X-ray diffraction and EXAFS. The hydrated vanadium(III) ion has a regular octahedral configuration with a mean V-O bond distance of 1.99 Å. In the hydrated and dimethylsulfoxide solvated oxovanadium(IV) ions vanadium binds strongly to an oxo group at ca. 1.6 Å. The solvent molecule trans to the oxo group is very weakly bound, at ca. 2.2 Å, while the remaining four solvent molecules, with a mean V-O bond distance of 2.0 Å, form a plane slightly below the vanadium atom; the mean O=V-Operp bond angle is ca. 98°. In the dmpu solvated oxovanadium(IV) ion, the space demanding properties of the dmpu molecule leaving no solvent molecule in the trans position to the oxo group which reduces the coordination number to 5. The O=V-O bond angle is consequently much larger, 106°, and the mean V=O and V-O bond distances decrease to 1.58 and 1.97 Å, respectively. The hydrated and dimethylsulfoxide solvated dioxovanadium(V) ions display a very distorted octahedral configuration with the oxo groups in cis position with mean V=O bond distances of 1.6 Å and a O=V=O bond angle of ca. 105°. The solvent molecules trans to the oxo groups are weakly bound, at ca. 2.2 Å, while the remaining two have bond distances of 2.02 Å. The experimental studies of the coordination chemistry of hydrated and solvated vanadium(III,IV,V) ions are complemented by summarizing previously reported crystal structures to yield a comprehensive description of the coordination chemistry of vanadium with oxygen donor ligands. PMID:22950803

Demonstration of Ion Kinetic Effects in Inertial Confinement Fusion Implosions and Investigation of Magnetic Reconnection Using Laser-Produced Plasmas

NASA Astrophysics Data System (ADS)

Rosenberg, M. J.

2016-10-01

Shock-driven laser inertial confinement fusion (ICF) implosions have demonstrated the presence of ion kinetic effects in ICF implosions and also have been used as a proton source to probe the strongly driven reconnection of MG magnetic fields in laser-generated plasmas. Ion kinetic effects arise during the shock-convergence phase of ICF implosions when the mean free path for ion-ion collisions (λii) approaches the size of the hot-fuel region (Rfuel) and may impact hot-spot formation and the possibility of ignition. To isolate and study ion kinetic effects, the ratio of N - K =λii /Rfuel was varied in D3He-filled, shock-driven implosions at the Omega Laser Facility and the National Ignition Facility, from hydrodynamic-like conditions (NK 0.01) to strongly kinetic conditions (NK 10). A strong trend of decreasing fusion yields relative to the predictions of hydrodynamic models is observed as NK increases from 0.1 to 10. Hydrodynamics simulations that include basic models of the kinetic effects that are likely to be present in these experiments-namely, ion diffusion and Knudsen-layer reduction of the fusion reactivity-are better able to capture the experimental results. This type of implosion has also been used as a source of monoenergetic 15-MeV protons to image magnetic fields driven to reconnect in laser-produced plasmas at conditions similar to those encountered at the Earth's magnetopause. These experiments demonstrate that for both symmetric and asymmetric magnetic-reconnection configurations, when plasma flows are much stronger than the nominal Alfvén speed, the rate of magnetic-flux annihilation is determined by the flow velocity and is largely insensitive to initial plasma conditions. This work was supported by the Department of Energy Grant Number DENA0001857.

2D polymeric cadmium(II) complexes containing 1,3-imidazolidine-2-thione (Imt) ligand, [Cd(Imt)(H2O)2(SO4)]n and [Cd(Imt)2(N3)2]n

NASA Astrophysics Data System (ADS)

Mahmood, Rashid; Ahmad, Saeed; Fettouhi, Mohammed; Roisnel, Thierry; Gilani, Mazhar Amjad; Mehmood, Kashif; Murtaza, Ghulam; Isab, Anvarhusein A.

2018-03-01

The present study aims at preparing and carrying out the structural investigation of two polymeric cadmium(II) complexes of imidazolidine-2-thione (Imt) based on sulfate or azide ions, [Cd(Imt)(H2O)2(SO4)]n (1) and [Cd(Imt)2(N3)2]n (2). The structures of the complexes were determined by single crystal X-ray analysis. Both compounds, 1 and 2 crystallize in the form of 2D coordination polymers and the cadmium(II) ion is six-coordinate having a distorted octahedral geometry in each compound. In 1, the metal ion is bonded to one sulfur atom of Imt and five oxygen atoms with two from water and three of bridging sulfate ions. In 2, the cadmium coordination sphere is completed by two Imt molecules binding through the sulfur atoms and four nitrogen atoms of bridging azide ions. The crystal structures are stabilized by intra and intermolecular hydrogen bonding interactions. The complexes were also characterized by IR and NMR spectroscopy and the spectroscopic data is consistent with the binding of the ligands.

Electro-diffusion in a plasma with two ion species

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

Kagan, Grigory; Tang Xianzhu

2012-08-15

Electric field is a thermodynamic force that can drive collisional inter-ion-species transport in a multicomponent plasma. In an inertial confinement fusion capsule, such transport causes fuel ion separation even with a target initially prepared to have equal number densities for the two fuel ion species. Unlike the baro-diffusion driven by ion pressure gradient and the thermo-diffusion driven by ion and electron temperature gradients, electro-diffusion has a critical dependence on the charge-to-mass ratio of the ion species. Specifically, it is shown here that electro-diffusion vanishes if the ion species have the same charge-to-mass ratio. An explicit expression for the electro-diffusion ratiomore » is obtained and used to investigate the relative importance of electro- and baro-diffusion mechanisms. In particular, it is found that electro-diffusion reinforces baro-diffusion in the deuterium and tritium mix, but tends to cancel it in the deuterium and helium-3 mix.« less

Co(II) Coordination in Prokaryotic Zinc Finger Domains as Revealed by UV-Vis Spectroscopy

PubMed Central

Sivo, Valeria; D'Abrosca, Gianluca; Russo, Luigi; Iacovino, Rosa; Pedone, Paolo Vincenzo; Fattorusso, Roberto

2017-01-01

Co(II) electronic configuration allows its use as a spectroscopic probe in UV-Vis experiments to characterize the metal coordination sphere that is an essential component of the functional structure of zinc-binding proteins and to evaluate the metal ion affinities of these proteins. Here, exploiting the capability of the prokaryotic zinc finger to use different combinations of residues to properly coordinate the structural metal ion, we provide the UV-Vis characterization of Co(II) addition to Ros87 and its mutant Ros87_C27D which bears an unusual CysAspHis2 coordination sphere. Zinc finger sites containing only one cysteine have been infrequently characterized. We show for the CysAspHis2 coordination an intense d-d transition band, blue-shifted with respect to the Cys2His2 sphere. These data complemented by NMR and CD data demonstrate that the tetrahedral geometry of the metal site is retained also in the case of a single-cysteine coordination sphere. PMID:29386985

Co(II) Coordination in Prokaryotic Zinc Finger Domains as Revealed by UV-Vis Spectroscopy.

PubMed

Sivo, Valeria; D'Abrosca, Gianluca; Russo, Luigi; Iacovino, Rosa; Pedone, Paolo Vincenzo; Fattorusso, Roberto; Isernia, Carla; Malgieri, Gaetano

2017-01-01

Co(II) electronic configuration allows its use as a spectroscopic probe in UV-Vis experiments to characterize the metal coordination sphere that is an essential component of the functional structure of zinc-binding proteins and to evaluate the metal ion affinities of these proteins. Here, exploiting the capability of the prokaryotic zinc finger to use different combinations of residues to properly coordinate the structural metal ion, we provide the UV-Vis characterization of Co(II) addition to Ros87 and its mutant Ros87_C27D which bears an unusual CysAspHis 2 coordination sphere. Zinc finger sites containing only one cysteine have been infrequently characterized. We show for the CysAspHis 2 coordination an intense d - d transition band, blue-shifted with respect to the Cys 2 His 2 sphere. These data complemented by NMR and CD data demonstrate that the tetrahedral geometry of the metal site is retained also in the case of a single-cysteine coordination sphere.

Development progresses of radio frequency ion source for neutral beam injector in fusion devices.

PubMed

Chang, D H; Jeong, S H; Kim, T S; Park, M; Lee, K W; In, S R

2014-02-01

A large-area RF (radio frequency)-driven ion source is being developed in Germany for the heating and current drive of an ITER device. Negative hydrogen ion sources are the major components of neutral beam injection systems in future large-scale fusion experiments such as ITER and DEMO. RF ion sources for the production of positive hydrogen (deuterium) ions have been successfully developed for the neutral beam heating systems at IPP (Max-Planck-Institute for Plasma Physics) in Germany. The first long-pulse ion source has been developed successfully with a magnetic bucket plasma generator including a filament heating structure for the first NBI system of the KSTAR tokamak. There is a development plan for an RF ion source at KAERI to extract the positive ions, which can be applied for the KSTAR NBI system and to extract the negative ions for future fusion devices such as the Fusion Neutron Source and Korea-DEMO. The characteristics of RF-driven plasmas and the uniformity of the plasma parameters in the test-RF ion source were investigated initially using an electrostatic probe.

Liquid electrolyte informatics using an exhaustive search with linear regression.

PubMed

Sodeyama, Keitaro; Igarashi, Yasuhiko; Nakayama, Tomofumi; Tateyama, Yoshitaka; Okada, Masato

2018-06-14

Exploring new liquid electrolyte materials is a fundamental target for developing new high-performance lithium-ion batteries. In contrast to solid materials, disordered liquid solution properties have been less studied by data-driven information techniques. Here, we examined the estimation accuracy and efficiency of three information techniques, multiple linear regression (MLR), least absolute shrinkage and selection operator (LASSO), and exhaustive search with linear regression (ES-LiR), by using coordination energy and melting point as test liquid properties. We then confirmed that ES-LiR gives the most accurate estimation among the techniques. We also found that ES-LiR can provide the relationship between the "prediction accuracy" and "calculation cost" of the properties via a weight diagram of descriptors. This technique makes it possible to choose the balance of the "accuracy" and "cost" when the search of a huge amount of new materials was carried out.

Laser-driven ion acceleration at BELLA

NASA Astrophysics Data System (ADS)

Bin, Jianhui; Steinke, Sven; Ji, Qing; Nakamura, Kei; Treffert, Franziska; Bulanov, Stepan; Roth, Markus; Toth, Csaba; Schroeder, Carl; Esarey, Eric; Schenkel, Thomas; Leemans, Wim

2017-10-01

BELLA is a high repetiton rate PW laser and we used it for high intensity laser plasma acceleration experiments. The BELLA-i program is focused on relativistic laser plasma interaction such as laser driven ion acceleration, aiming at establishing an unique collaborative research facility providing beam time to selected external groups for fundamental physics and advanced applications. Here we present our first parameter study of ion acceleration driven by the BELLA-PW laser with truly high repetition rate. The laser repetition rate of 1Hz allows for scanning the laser pulse duration, relative focus location and target thickness for the first time at laser peak powers of above 1 PW. Furthermore, the long focal length geometry of the experiment (f ∖65) and hence, large focus size provided ion beams of reduced divergence and unprecedented charge density. This work was supported by the Director, Office of Science, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

ISEE 1 observations of electrostatic ion cyclotron waves in association with ion beams on auroral field lines from about 2.5 to 4.5 R(E)

NASA Technical Reports Server (NTRS)

Catell, C. A.; Mozer, F. S.; Roth, I.; Anderson, R. R.; Elphic, R. C.

1991-01-01

Quasi-monochromatic waves at about the hydrogen cyclotron frequency were observed as the ISEE 1 satellite traversed auroral field lines at radial distances of about 2.5-4.5 R(E) near midnight on June 19, 1981. Waves and both lower and higher frequencies were observed at higher altitudes, and possible electrostatic helium cyclotron and oxygen cyclotron waves occurred at lower altitudes. Upflowing hydrogen and oxygen beams and field-aligned currents occurred simultaneously. The features of the waves are most consistent with the current-driven mode. In addition, numerical studies of the linear dispersion relation, using parameters based on the observations, show that both the parallel and oblique two-stream modes and the ion-beam-driven modes were stable while oblique current-driven modes were unstable. The O(+) and H(+) distributions provide evidence for interactions with local electrostatic ion cyclotron waves and for the H(+)-O(+) two-stream instability at altitudes below the satellite.

Porphyrin framework solids. Synthesis and structure of hybrid coordination polymers of tetra(carboxyphenyl)porphyrins and lanthanide-bridging ions.

PubMed

Muniappan, Sankar; Lipstman, Sophia; George, Sumod; Goldberg, Israel

2007-07-09

New types of porphyrin-based framework solids were constructed by reacting meso-tetra(3-carboxyphenyl)porphyrin and meso-tetra(4-carboxyphenyl)metalloporphyrins with common salts of lanthanide metal ions. The large size, high coordination numbers and strong affinity for oxo ligands of the latter, combined with favorable hydrothermal reaction conditions, allowed the formation of open three-dimensional single-framework architectures by coordination polymerization, in which the tetradentate porphyrin units are intercoordinated by multinuclear assemblies of the bridging metal ions. The latter serve as construction pillars of the supramolecular arrays, affording stable structures. Several modes of coordination polymerization were revealed by single-crystal X-ray diffraction. They differ by the spatial functionality of the porphyrin building blocks, the coordination patterns of the lanthanide-carboxylate assemblies, and the topology of the resulting frameworks. The seven new reported structures exhibit periodically spaced 0.4-0.6 nm wide channel voids that perforate the respective crystalline polymeric architectures and are accessible to solvent components. Materials based on the m-carboxyphenyl derivative reveal smaller channels than those based on the p-carboxyphenyl analogues. An additional complex of the former with a smaller third-row transition metal (Co) is characterized by coordination connectivity in two dimensions only. Thermal and powder-diffraction analyses confirm the stability of the lanthanide-TmCPP (TmCPP=tetra(m-carboxyphenyl)porphyrin) frameworks.

Flexible Reactive Berm (FRBerm) for Removal of Heavy Metals from Runoff Water

DTIC Science & Technology

2016-03-01

FRTR) include precipitation and flocculation, treatment with ion exchange resins, and phytoremediation . The costs of these technologies are driven by... phytoremediation (http://www.frtr.gov, accessed 11 November 2015). The costs of these technologies are driven by the size and complexity of the site...precipitation and flocculation, treatment with ion exchange resins, and phytoremediation (http://www.frtr.gov, accessed 11 November 2015). The

Structural Transformation of Guanine Coordination Motifs in Water Induced by Metal ions and Temperature.

PubMed

Li, Wei; Jin, Jing; Liu, Xiaoqing; Wang, Li

2018-06-15

The transformation effects of metal ions and temperature on the DNA bases guanine (G) metal-organic coordination motifs in water have been investigated by scanning tunneling microcopy (STM). The G molecules form an ordered hydrogen-bonded structure at the water- highly oriented pyrolytic graphite (HOPG) interface. The STM observations reveal that the canonical G/9H form can be transformed into the G/(3H, 7H) tautomer by increasing the temperature of the G solution to 38.6oC. Moreover, metal ions bind with G molecules to form G4Fe13+, G3Fe32+ and the heterochiral intermixed G4Na1+ metal-organic networks after the introduction of the alkali-metal ions in cellular environment.

Syntheses, crystal structures, and properties of six new lanthanide(III) transition metal tellurium(IV) oxyhalides with three types of structures.

PubMed

Shen, Yue-Ling; Mao, Jiang-Gao

2005-07-25

Solid-state reactions of lanthanide(III) oxide (and lanthanide(III) oxyhalide), transition metal halide (and transition metal oxide), and TeO(2) at high temperature lead to six new lanthanide transition metal tellurium(IV) oxyhalides with three different types of structures, namely, DyCuTe(2)O(6)Cl, ErCuTe(2)O(6)Cl, ErCuTe(2)O(6)Br, Sm(2)Mn(Te(5)O(13))Cl(2), Dy(2)Cu(Te(5)O(13))Br(2), and Nd(4)Cu(TeO(3))(5)Cl(3). Compounds DyCuTe(2)O(6)Cl, ErCuTe(2)O(6)Cl, and ErCuTe(2)O(6)Br are isostructural. The lanthanide(III) ion is eight-coordinated by eight oxygen atoms, and the copper(II) ion is five-coordinated by four oxygens and a halide anion in a distorted square pyramidal geometry. The interconnection of Ln(III) and Cu(II) ions by bridging tellurite anions results in a three-dimensional (3D) network with tunnels along the a-axis; the halide anion and the lone-pair electrons of the tellurium(IV) ions are oriented toward the cavities of the tunnels. Compounds Sm(2)Mn(Te(5)O(13))Cl(2) and Dy(2)Cu(Te(5)O(13))Br(2) are isostructural. The lanthanide(III) ions are eight-coordinated by eight oxygens, and the divalent transition metal ion is octahedrally coordinated by six oxygens. Two types of polymeric tellurium(IV) oxide anions are formed: Te(3)O(8)(4)(-) and Te(4)O(10)(4)(-). The interconnection of the lanthanide(III) and divalent transition metal ions by the above two types of polymeric tellurium(IV) oxide anions leads to a 3D network with long, narrow-shaped tunnels along the b-axis. The halide anions remain isolated and are located at the above tunnels. Nd(4)Cu(TeO(3))(5)Cl(3) features a different structure. All five of the Nd(III) ions are eight-coordinated (NdO(8) for Nd(1), Nd(2), Nd(4), and Nd(5) and NdO(7)Cl for Nd(3)), and the copper(I) ion is tetrahedrally coordinated by four chloride anions. The interconnection of Nd(III) ions by bridging tellurite anions resulted in a 3D network with large tunnels along the b-axis. The CuCl(4) tetrahedra are interconnected into a 1D two-unit repeating (zweier) chain via corner-sharing. These 1D copper(I) chloride chains are inserted into the tunnels of the neodymium(III) tellurite via Nd-Cl-Cu bridges. Luminescent studies show that ErCuTe(2)O(6)Cl and Nd(4)Cu(TeO(3))(5)Cl(3) exhibit strong luminescence in the near-IR region. Magnetic measurements indicate the antiferromagnetic interactions between magnetic centers in these compounds.

An analytically solvable three-body break-up model problem in hyperspherical coordinates

NASA Astrophysics Data System (ADS)

Ancarani, L. U.; Gasaneo, G.; Mitnik, D. M.

2012-10-01

An analytically solvable S-wave model for three particles break-up processes is presented. The scattering process is represented by a non-homogeneous Coulombic Schrödinger equation where the driven term is given by a Coulomb-like interaction multiplied by the product of a continuum wave function and a bound state in the particles coordinates. The closed form solution is derived in hyperspherical coordinates leading to an analytic expression for the associated scattering transition amplitude. The proposed scattering model contains most of the difficulties encountered in real three-body scattering problem, e.g., non-separability in the electrons' spherical coordinates and Coulombic asymptotic behavior. Since the coordinates' coupling is completely different, the model provides an alternative test to that given by the Temkin-Poet model. The knowledge of the analytic solution provides an interesting benchmark to test numerical methods dealing with the double continuum, in particular in the asymptotic regions. An hyperspherical Sturmian approach recently developed for three-body collisional problems is used to reproduce to high accuracy the analytical results. In addition to this, we generalized the model generating an approximate wave function possessing the correct radial asymptotic behavior corresponding to an S-wave three-body Coulomb problem. The model allows us to explore the typical structure of the solution of a three-body driven equation, to identify three regions (the driven, the Coulombic and the asymptotic), and to analyze how far one has to go to extract the transition amplitude.

Synthesis, structures and fluorescent properties of two novel lanthanide [Ln = Ce(III), Pr(III)] coordination polymers based on 1,3-benzenedicarboxylate and 2-(4-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline ligands

NASA Astrophysics Data System (ADS)

Wang, Lei; Ni, Liang; yao, Jia

2012-09-01

Two structurally diverse coordination polymers [Ce2(m-BDC)2(m-HBDC)2(MOPIP)2·3/2H2O]n (1) and [Pr2(m-BDC)3(MOPIP)2·H2O]n(2) have been synthesized by hydrothermal reaction of lanthanide chloride with mixed ligands benzene-1,3-dicarboxylic acid and 2-(4-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline (MOPIP). The crystal structures of the complexes are zipper-like chains of octacoordinate Ln3+ ions, in which Ln3+ ions are bridged in different coordination modes by m-BDC2+ and decorated by MOPIP ligands. These chains are further assembled into three-dimensional supramolecular framework by π⋯π stacking and hydrogen bonding interactions. The fluorescent property and thermal stability were also investigated. Additionally, Natural bond orbital (NBO) analysis of complex 2 shows a weak covalent interaction between the coordinated atoms and Pr3+ ions.

Insight into the coordination and the binding sites of Cu(2+) by the histidyl-6-tag using experimental and computational tools.

PubMed

Watly, Joanna; Simonovsky, Eyal; Wieczorek, Robert; Barbosa, Nuno; Miller, Yifat; Kozlowski, Henryk

2014-07-07

His-tags are specific sequences containing six to nine subsequent histydyl residues, and they are used for purification of recombinant proteins by use of IMAC chromatography. Such polyhistydyl tags, often used in molecular biology, can be also found in nature. Proteins containing histidine-rich domains play a critical role in many life functions in both prokaryote and eukaryote organisms. Binding mode and the thermodynamic properties of the system depend on the specific metal ion and the histidine sequence. Despite the wide application of the His-tag for purification of proteins, little is known about the properties of metal-binding to such tag domains. This inspired us to undertake detailed studies on the coordination of Cu(2+) ion to hexa-His-tag. Experiments were performed using the potentiometric, UV-visible, CD, and EPR techniques. In addition, molecular dynamics (MD) simulations and density functional theory (DFT) calculations were applied. The experimental studies have shown that the Cu(2+) ion binds most likely to two imidazoles and one, two, or three amide nitrogens, depending on the pH. The structures and stabilities of the complexes for the Cu(2+)-Ac-(His)6-NH2 system using experimental and computational tools were established. Polymorphic binding states are suggested, with a possibility of the formation of α-helix structure induced by metal ion coordination. Metal ion is bound to various pairs of imidazole moieties derived from the tag with different efficiencies. The coordination sphere around the metal ion is completed by molecules of water. Finally, the Cu(2+) binding by Ac-(His)6-NH2 is much more efficient compared to other multihistidine protein domains.

Time Independent Functional task Training: a case study on the effect of inter-joint coordination driven haptic guidance in stroke therapy.

PubMed

Brokaw, Elizabeth B; Murray, Theresa M; Nef, Tobias; Lum, Peter S; Brokaw, Elizabeth B; Nichols, Diane; Holley, Rahsaan J

2011-01-01

After a stroke abnormal joint coordination of the arm may limit functional movement and recovery. To aid in training inter-joint movement coordination a haptic guidance method for functional driven rehabilitation after stroke called Time Independent Functional Training (TIFT) has been developed for the ARMin III robot. The mode helps retraining inter-joint coordination during functional movements, such as putting an object on a shelf, pouring from a pitcher, and sorting objects into bins. A single chronic stroke subject was tested for validation of the modality. The subject was given 1.5 hrs of robotic therapy twice a week for 4 weeks. The therapy and the results of training the single stroke subject are discussed. The subject showed a decrease in training joint error for the sorting task across training sessions and increased self-selected movement time in training. In kinematic reaching analysis the subject showed improvements in range of motion and joint coordination in a reaching task, as well as improvements in supination-pronation range of motion at the wrist. © 2011 IEEE

Efficient quasi-monoenergetic ion beams from laser-driven relativistic plasmas

PubMed Central

Palaniyappan, Sasi; Huang, Chengkun; Gautier, Donald C.; Hamilton, Christopher E.; Santiago, Miguel A.; Kreuzer, Christian; Sefkow, Adam B.; Shah, Rahul C.; Fernández, Juan C.

2015-01-01

Table-top laser–plasma ion accelerators have many exciting applications, many of which require ion beams with simultaneous narrow energy spread and high conversion efficiency. However, achieving these requirements has been elusive. Here we report the experimental demonstration of laser-driven ion beams with narrow energy spread and energies up to 18 MeV per nucleon and ∼5% conversion efficiency (that is 4 J out of 80-J laser). Using computer simulations we identify a self-organizing scheme that reduces the ion energy spread after the laser exits the plasma through persisting self-generated plasma electric (∼1012 V m−1) and magnetic (∼104 T) fields. These results contribute to the development of next generation compact accelerators suitable for many applications such as isochoric heating for ion-fast ignition and producing warm dense matter for basic science. PMID:26657147

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

Luo, Qingtao; Li, Liyu; Nie, Zimin

We will show a new method to differentiate the vanadium transport from concentration gradient and that from electric field. Flow batteries with vanadium and iron redox couples as the electro-active species were employed to investigate the transport behavior of vanadium ions in the presence of electric field. It was shown that electric field accelerated the positive-to-negative and reduced the negative-to-positive vanadium ions transport in charge process and affected the vanadium ions transport in an opposite way in discharge process. In addition, a method was designed to differentiate the concentration gradient-driven vanadium ions diffusion and electric field-driven vanadium ions migration. Simplifiedmore » mathematical model was established to simulate the vanadium ions transport in real charge-discharge operation of flow battery. The concentration gradient diffusion coefficients and electric-migration coefficients of V2+, V3+, VO2+, and VO2+ across Nafion membrane were obtained by fitting the experimental data.« less

Effect of plasma grid bias on extracted currents in the RF driven surface-plasma negative ion source

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

Belchenko, Yu., E-mail: belchenko@inp.nsk.su; Ivanov, A.; Sanin, A.

2016-02-15

Extraction of negative ions from the large inductively driven surface-plasma negative ion source was studied. The dependencies of the extracted currents vs plasma grid (PG) bias potential were measured for two modifications of radio-frequency driver with and without Faraday screen, for different hydrogen feeds and for different levels of cesium conditioning. The maximal PG current was independent of driver modification and it was lower in the case of inhibited cesium. The maximal extracted negative ion current depends on the potential difference between the near-PG plasma and the PG bias potentials, while the absolute value of plasma potential in the drivermore » and in the PG area is less important for the negative ion production. The last conclusion confirms the main mechanism of negative ion production through the surface conversion of fast atoms.« less

Efficient quasi-monoenergetic ion beams from laser-driven relativistic plasmas

DOE PAGES

Palaniyappan, Sasi; Huang, Chengkun; Gautier, Donald C.; ...

2015-12-11

Here, table-top laser–plasma ion accelerators have many exciting applications, many of which require ion beams with simultaneous narrow energy spread and high conversion efficiency. However, achieving these requirements has been elusive. Here we report the experimental demonstration of laser-driven ion beams with narrow energy spread and energies up to 18 MeV per nucleon and ~5% conversion efficiency (that is 4 J out of 80-J laser). Using computer simulations we identify a self-organizing scheme that reduces the ion energy spread after the laser exits the plasma through persisting self-generated plasma electric (~10 12 V m –1) and magnetic (~10 4 T)more » fields. These results contribute to the development of next generation compact accelerators suitable for many applications such as isochoric heating for ion-fast ignition and producing warm dense matter for basic science.« less

Negative ion-driven associated particle neutron generator

DOE PAGES

Antolak, A. J.; Leung, K. N.; Morse, D. H.; ...

2015-10-09

We describe an associated particle neutron generator that employs a negative ion source to produce high neutron flux from a small source size. Furthermore, negative ions produced in an rf-driven plasma source are extracted through a small aperture to form a beam which bombards a positively biased, high voltage target electrode. Electrons co-extracted with the negative ions are removed by a permanent magnet electron filter. The use of negative ions enables high neutron output (100% atomic ion beam), high quality imaging (small neutron source size), and reliable operation (no high voltage breakdowns). Finally, the neutron generator can operate in eithermore » pulsed or continuous-wave (cw) mode and has been demonstrated to produce 10 6 D-D n/s (equivalent to similar to 10 8 D-T n/s) from a 1 mm-diameter neutron source size to facilitate high fidelity associated particle imaging.« less

Tris{2-meth­oxy-6-[(4-methyl­phen­yl)iminiometh­yl]phenolate-κ2 O,O′}tris­(thio­cyanato-κN)europium(III)

PubMed Central

Liu, Jian-Feng; Liu, Jia-Lu; Zhao, Guo-Liang

2009-01-01

The metal center in the structure of the title compound, [Eu(NCS)3(C15H15NO2)3], is coordinated by three Schiff base 2-meth­oxy-6-[(4-methyl­phen­yl)iminiometh­yl]phenolate (L) ligands and three independent thio­cyanate ions. In the crystal structure, the acidic H atom is located on the Schiff base N atom and hydrogen bonded to the phenolate O atom. The coordination environment of the EuIII ion is nine-coordinate by three chelating methoxy­phenolate pairs of O atoms and three N-atom terminals of the thio­cyanate ions. The compound is isostructural with the CeIII analogue [Liu et al. (2009 ▶). Acta Cryst. E65, m650]. PMID:21578663

Importance of counteranions on the hydration structure of the curium ion

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

Atta Fynn, Raymond; Bylaska, Eric J.; De Jong, Wibe A.

2013-07-04

Using density functional theory based ab initio molecular dynamics and metadynamics we show that counter ions can trigger noticeable changes in the hydration shell structure of the curium ion. The free energies of curium-water coordination and the solvent hydrogen bond (HB) lifetimes in the absence and presence the counter anions predict that chloride and bromide counter anions strengthen the first shell and consequently the 8-fold coordination state is dominant by at least 98%. In contrast, the perchlorate counter anions are found to weaken the coordination shell and the HB network, with the 9-fold and 8-fold states existing in an 8:1more » ratio, which is in good agreement with reported 9:1 ratio seen in time resolved fluorescence spectroscopy experiments. To our knowledge this is the first time molecular simulations have shown that counter anions can directly affect the first hydration shell structure of a cation.« less

The biological inorganic chemistry of zinc ions.

PubMed

Krężel, Artur; Maret, Wolfgang

2016-12-01

The solution and complexation chemistry of zinc ions is the basis for zinc biology. In living organisms, zinc is redox-inert and has only one valence state: Zn(II). Its coordination environment in proteins is limited by oxygen, nitrogen, and sulfur donors from the side chains of a few amino acids. In an estimated 10% of all human proteins, zinc has a catalytic or structural function and remains bound during the lifetime of the protein. However, in other proteins zinc ions bind reversibly with dissociation and association rates commensurate with the requirements in regulation, transport, transfer, sensing, signalling, and storage. In contrast to the extensive knowledge about zinc proteins, the coordination chemistry of the "mobile" zinc ions in these processes, i.e. when not bound to proteins, is virtually unexplored and the mechanisms of ligand exchange are poorly understood. Knowledge of the biological inorganic chemistry of zinc ions is essential for understanding its cellular biology and for designing complexes that deliver zinc to proteins and chelating agents that remove zinc from proteins, for detecting zinc ion species by qualitative and quantitative analysis, and for proper planning and execution of experiments involving zinc ions and nanoparticles such as zinc oxide (ZnO). In most investigations, reference is made to zinc or Zn 2+ without full appreciation of how biological zinc ions are buffered and how the d-block cation Zn 2+ differs from s-block cations such as Ca 2+ with regard to significantly higher affinity for ligands, preference for the donor atoms of ligands, and coordination dynamics. Zinc needs to be tightly controlled. The interaction with low molecular weight ligands such as water and inorganic and organic anions is highly relevant to its biology but in contrast to its coordination in proteins has not been discussed in the biochemical literature. From the discussion in this article, it is becoming evident that zinc ion speciation is important in zinc biochemistry and for biological recognition as a variety of low molecular weight zinc complexes have already been implicated in biological processes, e.g. with ATP, glutathione, citrate, ethylenediaminedisuccinic acid, nicotianamine, or bacillithiol. Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.

Metallosupramolecular Architectures Obtained from Poly-N-heterocyclic Carbene Ligands.

PubMed

Sinha, Narayan; Hahn, F Ekkehardt

2017-09-19

Over the past two decades, self-assembly of supramolecular architectures has become a field of intensive research due to the wide range of applications for the resulting assemblies in various fields such as molecular encapsulation, supramolecular catalysis, drug delivery, metallopharmaceuticals, chemical and photochemical sensing, and light-emitting materials. For these purposes, a large number of coordination-driven metallacycles and metallacages featuring different sizes and shapes have been prepared and investigated. Almost all of these are Werner-type coordination compounds where metal centers are coordinated by nitrogen and/or oxygen donors of polydentate ligands. With the evolving interest in the coordination chemistry of N-heterocyclic carbenes (NHCs), discrete supramolecular complexes held together by M-C NHC bonds have recently become of interest. The construction of such metallosupramolecular assemblies requires the synthesis of suitable poly-NHC ligands where the NHC donors form labile bonds with metal centers thus enabling the formation of the thermodynamically most stable reaction product. In organometallic chemistry, these conditions are uniquely met by the combination of poly-NHCs and silver(I) ions where the resulting assemblies also offer the possibility to generate new structures by transmetalation of the poly-NHC ligands to additional metal centers forming more stable C NHC -M bonds. Stable metallosupramolecular assemblies obtained from poly-NHC ligands feature special properties such as good solubility in many less polar organic solvents and the presence of the often catalyticlly active {M(NHC) n } moiety as building block. In this Account, we review recent developments in organometallic supramolecular architectures derived from poly-NHC ligands. We describe dinuclear (M = Ag I , Au I , Cu I ) tetracarbene complexes obtained from bis-NHC ligands with an internal olefin or two external coumarin pendants and their postsynthetic modification via a photochemically induced single or double [2 + 2] cycloaddition to form dinuclear tetracarbene complexes featuring cyclobutane units. Even three-dimensional cage-like structures can be prepared by this postsynthetic strategy. Cylinder-like trinuclear, tetranuclear, and hexanuclear (M = Ag I , Au I , Cu I , Hg II , Pd II ) complexes have been obtained from benzene-bridged tris-, tetrakis-, or hexakis-NHC ligands. These complexes resemble polynuclear assemblies obtained from related polydentate Werner-type ligands. Contrary to the Werner-type complexes, cylinder-like assemblies with three, four, or six silver(I) ions sandwiched in between two tris-, tetrakis-, or hexakis-NHC ligands undergo a facile transmetalation reaction to give the complexes featuring more stable M-C NHC bonds, normally with retention of the metallosupramolecular structure. This unique behavior of NHC-Ag + complexes allows the prepration of assemblies containing various metals from the poly-NHC silver(I) assemblies. Narcissistic self-sorting phenomena have also been observed for mixtures of selected poly-NHC ligands and silver(I) ions. Even a very early type of metallosupramolecular assembly, the tetranuclear molecular square, can be prepared from four bridging dicarbene ligands and four transition metal ions either by a stepwise assembly or by a single-step protocol. At this point, it appears that procedures for the synthesis of metallosupramolecular assemblies using polydentate Werner-type ligands and metal ions can be transferred to organometallic chemistry by using suitable poly-NHC ligands. The resulting structures feature stable M-C NHC bonds (with the exception of the labile C NHC -Ag + bond) when compared to M-N/M-O bonds in classical Werner-type complexes. The generally good solubility of the compounds and the presence of the often catalytically active {M(NHC) n } moiety make organometallic supramolecular complexes a promising new class of molecular hosts for catalytic transformations and encapsulation of selected substrates.

Copper(II) and zinc(II) as metal-carboxylate coordination complexes based on (1-methyl-1H-benzo[d]imidazol-2-yl) methanol derivative: Synthesis, crystal structure, spectroscopy, DFT calculations and antioxidant activity

NASA Astrophysics Data System (ADS)

Benhassine, Anfel; Boulebd, Houssem; Anak, Barkahem; Bouraiou, Abdelmalek; Bouacida, Sofiane; Bencharif, Mustapha; Belfaitah, Ali

2018-05-01

This work presents a combined experimental and theoretical study of two new metal-carboxylate coordination compounds. These complexes were prepared from (1-methyl-1H-benzimidazol-2-yl)methanol under mild conditions. The structures of the prepared compounds were characterized by single-crystal X-ray analysis, FTIR and UV-Vis spectroscopy. In the Cupper complex, the Cu(II) ion is coordinated by two ligands, which act as bidentate chelator through the non-substituted N and O atoms, and two carboxylicg oxygen atoms, displaying a hexa-coordinated compound in a distorted octahedral geometry, while in the Zinc complex the ligand is ligated to the Zn(II) ion in monodentate fashion through the N atom, and the metal ion is also bonded to carboxylic oxygen atoms. The tetra-coordinated compound displays a distorted tetrahedral shape. The density functional theory calculations are carried out for the determination of the optimized structures. The electronic transitions and fundamental vibrational wave numbers are calculated and are in good agreement with experimental. In addition, the ligand and its Cu(II) and Zn(II) complexes were screened and evaluated for their potential as DPPH radical scavenger.

Deconvolution of Raman spectroscopic signals for electrostatic, H-bonding, and inner-sphere interactions between ions and dimethyl phosphate in solution

PubMed Central

Christian, Eric L; Anderson, Vernon E.; Harris, Michael E

2011-01-01

Quantitative analysis of metal ion-phosphodiester interactions is a significant experimental challenge due to the complexities introduced by inner-sphere, outer-sphere (H-bonding with coordinated water), and electrostatic interactions that are difficult to isolate in solution studies. Here, we provide evidence that inner-sphere, H-bonding and electrostatic interactions between ions and dimethyl phosphate can be deconvoluted through peak fitting in the region of the Raman spectrum for the symmetric stretch of non-bridging phosphate oxygens (νsPO 2-). An approximation of the change in vibrational spectra due to different interaction modes is achieved using ions capable of all or a subset of the three forms of metal ion interaction. Contribution of electrostatic interactions to ion-induced changes to the Raman νsPO2- signal could be modeled by monitoring attenuation of νsPO2- in the presence of tetramethylammonium, while contribution of H-bonding and inner-sphere coordination could be approximated from the intensities of altered νsPO2- vibrational modes created by an interaction with ammonia, monovalent or divalent ions. A model is proposed in which discrete spectroscopic signals for inner-sphere, H-bonding, and electrostatic interactions are sufficient to account for the total observed change in νsPO2- signal due to interaction with a specific ion capable of all three modes of interaction. Importantly, the quantitative results are consistent with relative levels of coordination predicted from absolute electronegativity and absolute hardness of alkali and alkaline earth metals. PMID:21334281

Coordination ability determined transition metal ions substitution of Tb in Tb-Asp fluorescent nanocrystals and a facile ions-detection approach.

PubMed

Duan, Jiazhi; Ma, Baojin; Liu, Feng; Zhang, Shan; Wang, Shicai; Kong, Ying; Du, Min; Han, Lin; Wang, Jianjun; Sang, Yuanhua; Liu, Hong

2018-04-26

Although the synthesis and fluorescent properties of lanthanide-amino acid complex nanostructures have been investigated extensively, limited studies have been reported on metal ions' substitution ability for the lanthanide ions in the complex and their effect on the fluorescent property. In this study, taking biocompatible Tb-aspartic acid (Tb-Asp) complex nanocrystals as a model, the substitution mechanism of metal ions, particularly transition metals, for Tb ions in Tb-Asp nanocrystals and the change in the fluorescent property of the Tb-Asp nanocrystals after substitution were systematically investigated. The experimental results illustrated that metal ions with higher electronegativity, higher valence, and smaller radius possess stronger ability for Tb ions' substitution in Tb-Asp nanocrystals. Based on the effect of substituting ions' concentration on the fluorescent property of Tb-Asp, a facile method for copper ions detection with high sensitivity was proposed by measuring the fluorescent intensity of Tb-Asp nanocrystals' suspensions containing different concentrations of copper ions. The good biocompatibility, great convenience of synthesis and sensitive detection ability make Tb-Asp nanocrystals a very low cost and effective material for metal ions detection, which also opens a new door for practical applications of metal-Asp coordinated nanocrystals.

Crystal structure of [NaZn(BTC)(H2O)4]·1.5H2O (BTC = benzene-1,3,5-tri-carb-oxy-l-ate): a heterometallic coordination compound.

PubMed

Ni, Min; Li, Quanle; Chen, Hao; Li, Shengqing

2015-07-01

The title coordination polymer, poly[[μ-aqua-tri-aqua-(μ3-benzene-1,3,5-tri-carboxyl-ato)sodiumzinc] sesquihydrate], {[NaZn(C9H3O6)(H2O)4]·1.5H2O} n , was obtained in ionic liquid microemulsion at room temperture by the reaction of benzene-1,3,5-tri-carb-oxy-lic acid (H3BTC) with Zn(NO3)2·6H2O in the presence of NaOH. The asymmetric unit comprises two Na(+) ions (each located on an inversion centre), one Zn(2+) ion, one BTC ligand, four coordinating water mol-ecules and two solvent water molecules, one of which is disordered about an inversion centre and shows half-occupation. The Zn(2+) cation is five-coordinated by two carboxyl-ate O atoms from two different BTC ligands and three coordinating H2O mol-ecules; the Zn-O bond lengths are in the range 1.975 (2)-2.058 (3) Å. The Na(+) cations are six-coordinated but have different arrangements of the ligands: one is bound to two carboxyl-ate O atoms of two BTC ligands and four O atoms from four coordinating H2O mol-ecules while the other is bound by four carboxyl-ate O atoms from four BTC linkers and two O atoms of coordinating H2O mol-ecules. The completely deprotonated BTC ligand acts as a bridging ligand binding the Zn(2+) atom and Na(+) ions, forming a layered structure extending parallel to (100). An intricate network of O-H⋯O hydrogen bonds is present within and between the layers.

Speed of the bacterial flagellar motor near zero load depends on the number of stator units.

PubMed

Nord, Ashley L; Sowa, Yoshiyuki; Steel, Bradley C; Lo, Chien-Jung; Berry, Richard M

2017-10-31

The bacterial flagellar motor (BFM) rotates hundreds of times per second to propel bacteria driven by an electrochemical ion gradient. The motor consists of a rotor 50 nm in diameter surrounded by up to 11 ion-conducting stator units, which exchange between motors and a membrane-bound pool. Measurements of the torque-speed relationship guide the development of models of the motor mechanism. In contrast to previous reports that speed near zero torque is independent of the number of stator units, we observe multiple speeds that we attribute to different numbers of units near zero torque in both Na + - and H + -driven motors. We measure the full torque-speed relationship of one and two H + units in Escherichia coli by selecting the number of H + units and controlling the number of Na + units in hybrid motors. These experiments confirm that speed near zero torque in H + -driven motors increases with the stator number. We also measured 75 torque-speed curves for Na + -driven chimeric motors at different ion-motive force and stator number. Torque and speed were proportional to ion-motive force and number of stator units at all loads, allowing all 77 measured torque-speed curves to be collapsed onto a single curve by simple rescaling. Published under the PNAS license.

Speed of the bacterial flagellar motor near zero load depends on the number of stator units

PubMed Central

Nord, Ashley L.; Sowa, Yoshiyuki; Steel, Bradley C.; Lo, Chien-Jung; Berry, Richard M.

2017-01-01

The bacterial flagellar motor (BFM) rotates hundreds of times per second to propel bacteria driven by an electrochemical ion gradient. The motor consists of a rotor 50 nm in diameter surrounded by up to 11 ion-conducting stator units, which exchange between motors and a membrane-bound pool. Measurements of the torque–speed relationship guide the development of models of the motor mechanism. In contrast to previous reports that speed near zero torque is independent of the number of stator units, we observe multiple speeds that we attribute to different numbers of units near zero torque in both Na+- and H+-driven motors. We measure the full torque–speed relationship of one and two H+ units in Escherichia coli by selecting the number of H+ units and controlling the number of Na+ units in hybrid motors. These experiments confirm that speed near zero torque in H+-driven motors increases with the stator number. We also measured 75 torque–speed curves for Na+-driven chimeric motors at different ion-motive force and stator number. Torque and speed were proportional to ion-motive force and number of stator units at all loads, allowing all 77 measured torque–speed curves to be collapsed onto a single curve by simple rescaling. PMID:29078322

Observations of strong ion-ion correlations in dense plasmas

DOE PAGES

Ma, T.; Fletcher, L.; Pak, A.; ...

2014-04-24

Using simultaneous spectrally, angularly, and temporally resolved x-ray scattering, we measure the pronounced ion-ion correlation peak in a strongly coupled plasma. Laser-driven shock-compressed aluminum at ~3× solid density is probed with high-energy photons at 17.9 keV created by molybdenum He-α emission in a laser-driven plasma source. The measured elastic scattering feature shows a well-pronounced correlation peak at a wave vector of k=4Å –1. The magnitude of this correlation peak cannot be described by standard plasma theories employing a linear screened Coulomb potential. Advanced models, including a strong short-range repulsion due to the inner structure of the aluminum ions are howevermore » in good agreement with the scattering data. These studies have demonstrated a new highly accurate diagnostic technique to directly measure the state of compression and the ion-ion correlations. Furthermore, we have since applied this new method in single-shot wave-number resolved S(k) measurements to characterize the physical properties of dense plasmas.« less

Gas-phase study of new organozinc reagents by IRMPD-spectroscopy, computational modelling and tandem-MS.

PubMed

Massah, Ahmad R; Dreiocker, Frank; Jackson, Richard F W; Pickup, Barry T; Oomens, Jos; Meijer, Anthony J H M; Schäfer, Mathias

2011-08-07

An extensive set of organozinc iodides, useful for Negishi-type cross-coupling reactions, are investigated as respective cations after formal loss of iodide in the gas phase. Firstly, two new alkylzinc compounds derived from Tyrosine (Tyr) and Tryptophan (Trp) are closely examined. Secondly, the influence of specific protecting groups on the subtle balance between intra- and intermolecular coordination of zinc in these reagents is probed through trifluoroacetyl (TFA)-derivatized alkylzinc compounds. Finally, the influence of the strongly coordinating bidentate ligand N,N,N',N'-tetramethylethylenediamine (TMEDA) on the structure of alkylzinc cations is further explored in order to better understand the stability of the respective complexes towards water. A combination of electrospray (ESI)-MS/MS, accurate ion mass measurements, infrared multiple-photon dissociation (IRMPD) spectroscopy and computational modelling allowed the full characterisation of all dimethylformamide (DMF)-solvated and TMEDA-coordinated alkylzinc cations in the gas phase. The calculations indicate that the zinc cation in gas-phase alkylzinc-DMF or TMEDA-complex ions preferentially adopts a tetrahedral coordination sphere with four ligands. Additionally, conformers with only three binding partners bound to zinc but with effectively combined hydrogen-bond interactions are also found. Collision induced dissociation (CID) patterns demonstrate that the zinc-DMF interaction in tetrahedral four-coordinate mono-DMF-zinc complex ions as well as the interaction between TMEDA and zinc in the corresponding complex ions is even stronger than typical covalent bonds. In most cases, all major features of the IRMPD spectra are consistent with only a single major isomer, allowing secured identification and assignment. This journal is © the Owner Societies 2011

Modeling the Thermosphere as a Driven-Dissipative Thermodynamic System

DTIC Science & Technology

2013-03-01

8 Figure 2: Illustration of the geocentric solar magnetospheric coordinate system............15 Figure 3: Diagram of the...magnetic field in the z direction, Bz and the length of time Bz is in the negative z direction. The z direction is defined by Geocentric Solar...Magnetospheric (GSM) coordinates shown in Figure 2. Figure 2: Illustration of the geocentric solar magnetospheric (GSM) coordinate system. The origin is

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

PubMed

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

2016-06-01

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

Method and apparatus for plasma source ion implantation

DOEpatents

Conrad, J.R.

1988-08-16

Ion implantation into surfaces of three-dimensional targets is achieved by forming an ionized plasma about the target within an enclosing chamber and applying a pulse of high voltage between the target and the conductive walls of the chamber. Ions from the plasma are driven into the target object surfaces from all sides simultaneously without the need for manipulation of the target object. Repetitive pulses of high voltage, typically 20 kilovolts or higher, causes the ions to be driven deeply into the target. The plasma may be formed of a neutral gas introduced into the evacuated chamber and ionized therein with ionizing radiation so that a constant source of plasma is provided which surrounds the target object during the implantation process. Significant increases in the surface hardness and wear characteristics of various materials are obtained with ion implantation in this manner. 7 figs.

Method and apparatus for plasma source ion implantation

DOEpatents

Conrad, John R.

1988-01-01

Ion implantation into surfaces of three-dimensional targets is achieved by forming an ionized plasma about the target within an enclosing chamber and applying a pulse of high voltage between the target and the conductive walls of the chamber. Ions from the plasma are driven into the target object surfaces from all sides simultaneously without the need for manipulation of the target object. Repetitive pulses of high voltage, typically 20 kilovolts or higher, causes the ions to be driven deeply into the target. The plasma may be formed of a neutral gas introduced into the evacuated chamber and ionized therein with ionizing radiation so that a constant source of plasma is provided which surrounds the target object during the implantation process. Significant increases in the surface hardness and wear characteristics of various materials are obtained with ion implantation in this manner.

Desolvation-Driven 100-Fold Slow-down of Tunneling Relaxation Rate in Co(II)-Dy(III) Single-Molecule Magnets through a Single-Crystal-to-Single-Crystal Process

NASA Astrophysics Data System (ADS)

Liu, Jun-Liang; Wu, Jie-Yi; Huang, Guo-Zhang; Chen, Yan-Cong; Jia, Jian-Hua; Ungur, Liviu; Chibotaru, Liviu F.; Chen, Xiao-Ming; Tong, Ming-Liang

2015-11-01

Single-molecule magnets (SMMs) are regarded as a class of promising materials for spintronic and ultrahigh-density storage devices. Tuning the magnetic dynamics of single-molecule magnets is a crucial challenge for chemists. Lanthanide ions are not only highly magnetically anisotropic but also highly sensitive to the changes in the coordination environments. We developed a feasible approach to understand parts of the magneto-structure correlations and propose to regulate the relaxation behaviors via rational design. A series of Co(II)-Dy(III)-Co(II) complexes were obtained using in situ synthesis; in this system of complexes, the relaxation dynamics can be greatly improved, accompanied with desolvation, via single-crystal to single-crystal transformation. The effective energy barrier can be increased from 293 cm-1 (422 K) to 416 cm-1 (600 K), and the tunneling relaxation time can be grown from 8.5 × 10-4 s to 7.4 × 10-2 s. These remarkable improvements are due to the change in the coordination environments of Dy(III) and Co(II). Ab initio calculations were performed to better understand the magnetic dynamics.

The role of GyrB in the DNA cleavage-religation reaction of DNA gyrase: a proposed two metal-ion mechanism.

PubMed

Noble, Christian G; Maxwell, Anthony

2002-04-26

We have examined the role of the DNA gyrase B protein in cleavage and religation of DNA using site-directed mutagenesis. Three aspartate residues and a glutamate residue: E424, D498, D500 and D502, thought to co-ordinate a magnesium ion, were mutated to alanine; in addition, the glutamate residue and one aspartate residue were mutated to glutamine and asparagine, respectively. We have shown that these residues are important for the cleavage-religation reaction and are likely to be involved in magnesium ion co-ordination. On separate mutation of two of these aspartate residues to cysteine or histidine, the metal ion preference for the DNA relaxation activity of gyrase changed from magnesium to manganese (II). We present evidence to support the idea that cleavage of each DNA strand involves two or more metal ions, and suggest a scheme for the DNA cleavage chemistry of DNA gyrase involving two metal ions. (c) 2002 Elsevier Science Ltd.

Synthesis and Characterization of the Actinium Aquo Ion

PubMed Central

2017-01-01

Metal aquo ions occupy central roles in all equilibria that define metal complexation in natural environments. These complexes are used to establish thermodynamic metrics (i.e., stability constants) for predicting metal binding, which are essential for defining critical parameters associated with aqueous speciation, metal chelation, in vivo transport, and so on. As such, establishing the fundamental chemistry of the actinium(III) aquo ion (Ac-aquo ion, Ac(H2O)x3+) is critical for current efforts to develop 225Ac [t1/2 = 10.0(1) d] as a targeted anticancer therapeutic agent. However, given the limited amount of actinium available for study and its high radioactivity, many aspects of actinium chemistry remain poorly defined. We overcame these challenges using the longer-lived 227Ac [t1/2 = 21.772(3) y] isotope and report the first characterization of this fundamentally important Ac-aquo coordination complex. Our X-ray absorption fine structure study revealed 10.9 ± 0.5 water molecules directly coordinated to the AcIII cation with an Ac–OH2O distance of 2.63(1) Å. This experimentally determined distance was consistent with molecular dynamics density functional theory results that showed (over the course of 8 ps) that AcIII was coordinated by 9 water molecules with Ac–OH2O distances ranging from 2.61 to 2.76 Å. The data is presented in the context of other actinide(III) and lanthanide(III) aquo ions characterized by XAFS and highlights the uniqueness of the large AcIII coordination numbers and long Ac–OH2O bond distances. PMID:28386595

Poly[bis­[μ2-1,4-bis­(1H-imidazol-1-yl)butane]­dichloridonickel(II)

PubMed Central

Zhang, Jia; Song, Jiang-Feng

2011-01-01

The asymmetric unit of the title compound, [NiCl2(C10H14N4)2]n, consists of one Ni2+ ion which is located on an inversion center, one 1,4-bis­(imidazol-1-yl)butane (bimb) and one chloride ion. The Ni2+ ion exhibits a distorted octa­hedral coordination environment defined by four N atoms from four bimb ligands in the equatorial plane and two chloride ions in axial positions. The bridging coordination mode of the bimb ligands leads to the formation of inter­penetrating square Ni4(bimb)4 units that are arranged parallel to (001). The separation between the Ni atoms in these units is 13.740 (3) Å. PMID:22219855

Strong magneto-optical effects in A Cr2O4 (A =Fe,Co ) spinel oxides generated by tetrahedrally coordinated transition metal ions

NASA Astrophysics Data System (ADS)

Kocsis, V.; Bordács, S.; Deisenhofer, J.; Kiss, L. F.; Ohgushi, K.; Kaneko, Y.; Tokura, Y.; Kézsmárki, I.

2018-03-01

Magneto-optical effects have been investigated over the infrared visible spectral range in A Cr2O4 (A =Fe,Co ) spinel oxides with noncollinear spin orders in their ground states. We found large magneto-optical Kerr rotation and ellipticity at the on-site d -d transitions of the A2 + ions located within the charge gap. The magneto-optical Kerr rotation of ϑKerr≈12∘ observed in CoCr2O4 is unprecedentedly large among magnetic semiconductors and points toward the uniqueness of tetrahedrally coordinated Co2 + ions in generating strong magneto-optical response. Criteria of strong magneto-optical effects emerging at on-site d -d transitions of transition metal ions are discussed.

Tuning the Colors of the Dark Isomers of Photochromic Boron Compounds with Fluoride Ions: Four-State Color Switching.

PubMed

Mellerup, Soren K; Rao, Ying-Li; Amarne, Hazem; Wang, Suning

2016-09-02

Combining a three-coordinated boron (BMes2) moiety with a four-coordinated photochromic organoboron unit leads to a series of new diboron compounds that undergo four-state reversible color switching in response to stimuli of light, heat, and fluoride ions. Thus, these hybrid diboron systems allow both convenient color tuning/switching of such photochromic systems, as well as visual fluoride sensing by color or fluorescent emission color change.

Mechanical homeostasis of a DOPA-enriched biological coating from mussels in response to metal variation

PubMed Central

Schmitt, Clemens N. Z.; Winter, Alette; Bertinetti, Luca; Masic, Admir; Strauch, Peter; Harrington, Matthew J.

2015-01-01

Protein–metal coordination interactions were recently found to function as crucial mechanical cross-links in certain biological materials. Mussels, for example, use Fe ions from the local environment coordinated to DOPA-rich proteins to stiffen the protective cuticle of their anchoring byssal attachment threads. Bioavailability of metal ions in ocean habitats varies significantly owing to natural and anthropogenic inputs on both short and geological spatio-temporal scales leading to large variations in byssal thread metal composition; however, it is not clear how or if this affects thread performance. Here, we demonstrate that in natural environments mussels can opportunistically replace Fe ions in the DOPA coordination complex with V and Al. In vitro removal of the native DOPA–metal complexes with ethylenediaminetetraacetic acid and replacement with either Fe or V does not lead to statistically significant changes in cuticle performance, indicating that each metal ion is equally sufficient as a DOPA cross-linking agent, able to account for nearly 85% of the stiffness and hardness of the material. Notably, replacement with Al ions also leads to full recovery of stiffness, but only 82% recovery of hardness. These findings have important implications for the adaptability of this biological material in a dynamically changing and unpredictable habitat. PMID:26311314

High Anodic Performance of Co 1,3,5-Benzenetricarboxylate Coordination Polymers for Li-Ion Battery.

PubMed

Li, Chao; Lou, Xiaobing; Shen, Ming; Hu, Xiaoshi; Guo, Zhi; Wang, Yong; Hu, Bingwen; Chen, Qun

2016-06-22

We report the designed synthesis of Co 1,3,5-benzenetricarboxylate coordination polymers (CPs) via a straightforward hydrothermal method, in which three kinds of reaction solvents are selected to form CPs with various morphologies and dimensions. When tested as anode materials in Li-ion battery, the cycling stabilities of the three CoBTC CPs at a current density of 100 mA g(-1) have not evident difference; however, the reversible capacities are widely divergent when the current density is increased to 2 A g(-1). The optimized product CoBTC-EtOH maintains a reversible capacity of 473 mAh g(-1) at a rate of 2 A g(-1) after 500 galvanostatic charging/discharging cycles while retaining a nearly 100% Coulombic efficiency. The hollow microspherical morphology, accessible specific area, and the absence of coordination solvent of CoBTC-EtOH might be responsible for such difference. Furthermore, the ex situ soft X-ray absorption spectroscopy studies of CoBTC-EtOH under different states-of-charge suggest that the Co ions remain in the Co(2+) state during the charging/discharging process. Therefore, Li ions are inserted to the organic moiety (including the carboxylate groups and the benzene ring) of CoBTC without the direct engagement of Co ions during electrochemical cycling.

Preferential enhancement of laser-driven carbon ion acceleration from optimized nanostructured surfaces

PubMed Central

Dalui, Malay; Wang, W.-M.; Trivikram, T. Madhu; Sarkar, Subhrangshu; Tata, Sheroy; Jha, J.; Ayyub, P.; Sheng, Z. M.; Krishnamurthy, M.

2015-01-01

High-intensity ultrashort laser pulses focused on metal targets readily generate hot dense plasmas which accelerate ions efficiently and can pave way to compact table-top accelerators. Laser-driven ion acceleration studies predominantly focus on protons, which experience the maximum acceleration owing to their highest charge-to-mass ratio. The possibility of tailoring such schemes for the preferential acceleration of a particular ion species is very much desired but has hardly been explored. Here, we present an experimental demonstration of how the nanostructuring of a copper target can be optimized for enhanced carbon ion acceleration over protons or Cu-ions. Specifically, a thin (≈0.25 μm) layer of 25–30 nm diameter Cu nanoparticles, sputter-deposited on a polished Cu-substrate, enhances the carbon ion energy by about 10-fold at a laser intensity of 1.2×1018  W/cm2. However, particles smaller than 20 nm have an adverse effect on the ion acceleration. Particle-in-cell simulations provide definite pointers regarding the size of nanoparticles necessary for maximizing the ion acceleration. The inherent contrast of the laser pulse is found to play an important role in the species selective ion acceleration. PMID:26153048

Predicting neutron damage using TEM with in situ ion irradiation and computer modeling

NASA Astrophysics Data System (ADS)

Kirk, Marquis A.; Li, Meimei; Xu, Donghua; Wirth, Brian D.

2018-01-01

We have constructed a computer model of irradiation defect production closely coordinated with TEM and in situ ion irradiation of Molybdenum at 80 °C over a range of dose, dose rate and foil thickness. We have reexamined our previous ion irradiation data to assign appropriate error and uncertainty based on more recent work. The spatially dependent cascade cluster dynamics model is updated with recent Molecular Dynamics results for cascades in Mo. After a careful assignment of both ion and neutron irradiation dose values in dpa, TEM data are compared for both ion and neutron irradiated Mo from the same source material. Using the computer model of defect formation and evolution based on the in situ ion irradiation of thin foils, the defect microstructure, consisting of densities and sizes of dislocation loops, is predicted for neutron irradiation of bulk material at 80 °C and compared with experiment. Reasonable agreement between model prediction and experimental data demonstrates a promising direction in understanding and predicting neutron damage using a closely coordinated program of in situ ion irradiation experiment and computer simulation.

The Evolution of Ion Pumps.

ERIC Educational Resources Information Center

Maloney, Peter C.; Wilson, T. Hastings

1985-01-01

Constructs an evolutionary sequence to account for the diversity of ion pumps found today. Explanations include primary ion pumps in bacteria, features and distribution of ATP-driven pumps, preference for cation transport, and proton pump reversal. The integrated evolutionary hypothesis should encourage new experimental approaches. (DH)

Possible steric control of the relative strength of chelation enhanced fluorescence for zinc(II) compared to cadmium(II): metal ion complexing properties of tris(2-quinolylmethyl)amine, a crystallographic, UV-visible, and fluorometric study.

PubMed

Williams, Neil J; Gan, Wei; Reibenspies, Joseph H; Hancock, Robert D

2009-02-16

The idea is examined that steric crowding in ligands can lead to diminution of the chelation enhanced fluorescence (CHEF) effect in complexes of the small Zn(II) ion as compared to the larger Cd(II) ion. Steric crowding is less severe for the larger ion and for the smaller Zn(II) ion leads to Zn-N bond length distortion, which allows some quenching of fluorescence by the photoinduced electron transfer (PET) mechanism. Some metal ion complexing properties of the ligand tris(2-quinolylmethyl)amine (TQA) are presented in support of the idea that more sterically efficient ligands, which lead to less M-N bond length distortion with the small Zn(II) ion, will lead to a greater CHEF effect with Zn(II) than Cd(II). The structures of [Zn(TQA)H(2)O](ClO(4))(2).1.5 H(2)O (1), ([Pb(TQA)(NO(3))(2)].C(2)H(5)OH) (2), ([Ag(TQA)(ClO(4))]) (3), and (TQA).C(2)H(5)OH (4) are reported. In 1, the Zn(II) is 5-coordinate, with four N-donors from the ligand and a water molecule making up the coordination sphere. The Zn-N bonds are all of normal length, showing that the level of steric crowding in 1 is not sufficient to cause significant Zn-N bond length distortion. This leads to the observation that, as expected, the CHEF effect in the Zn(II)/TQA complex is much stronger than that in the Cd(II)/TQA complex, in contrast to similar but more sterically crowded ligands, where the CHEF effect is stronger in the Cd(II) complex. The CHEF effect for TQA with the metal ions examined varies as Zn(II) > Cd(II) > Ni(II) > Pb(II) > Hg(II) > Cu(II). The structure of 2 shows an 8-coordinate Pb(II), with evidence of a stereochemically active lone pair, and normal Pb-N bond lengths. In 3, the Ag(I) is 5-coordinate, with four N-donors from the TQA and an oxygen from the perchlorate. The Ag(I) shows no distortion toward linear 2-coordinate geometry, and the Ag-N bonds fall slightly into the upper range for Ag-N bonds in 5-coordinate complexes. The structure of 4 shows the TQA ligand to be involved in pi-stacking between quinolyl groups from adjacent TQA molecules. Formation constants determined by UV-visible spectroscopy are reported in 0.1 M NaClO(4) at 25 degrees C for TQA with Zn(II), Cd(II), and Pb(II). When compared with other similar ligands, one sees that, as the level of steric crowding increases, the stability decreases most with the small Zn(II) ion and least with the large Pb(II) ion. This is in accordance with the idea that TQA has a moderate level of steric crowding and that steric crowding increases for TQA analogs tris(2-pyridylmethyl)amine (TPyA) < TQA < tris(6-methyl-2-pyridyl)amine (TMPyA).

Ligand reprogramming in dinuclear helicate complexes: a consequence of allosteric or electrostatic effects?

PubMed

Jeffery, John C; Rice, Craig R; Harding, Lindsay P; Baylies, Christian J; Riis-Johannessen, Thomas

2007-01-01

The ditopic ligand 6,6'-bis(4-methylthiazol-2-yl)-3,3'-([18]crown-6)-2,2'-bipyridine (L(1)) contains both a potentially tetradentate pyridyl-thiazole (py-tz) N-donor chain and an additional "external" crown ether binding site which spans the central 2,2'-bipyridine unit. In polar solvents (MeCN, MeNO(2)) this ligand forms complexes with Zn(II), Cd(II), Hg(II) and Cu(I) ions via coordination of the N donors to the metal ion. Reaction with both Hg(II) and Cu(I) ions results in the self-assembly of dinuclear double-stranded helicate complexes. The ligands are partitioned by rotation about the central py--py bond, such that each can coordinate to both metals as a bis-bidentate donor ligand. With Zn(II) ions a single-stranded mononuclear species is formed in which one ligand coordinates the metal ion in a planar tetradentate fashion. Reaction with Cd(II) ions gives rise to an equilibrium between both the dinuclear double-stranded helicate and the mononuclear species. These complexes can further coordinate s-block metal cations via the remote crown ether O-donor domains; a consequence of which are some remarkable changes in the binding modes of the N-donor domains. Reaction of the Hg(II)- or Cd(II)-containing helicate with either Ba(2+) or Sr(2+) ions effectively reprogrammes the ligand to form only the single-stranded heterobinuclear complexes [MM'(L(1))](4+) (M=Hg(II), Cd(II); M'=Ba(2+), Sr(2+)), where the transition and s-block cations reside in the N- and O-donor sites, respectively. In contrast, the same ions have only a minor structural impact on the Zn(II) species, which already exists as a single-stranded mononuclear complex. Similar reactions with the Cd(II) system result in a shift in equilibrium towards the single-stranded species, the extent of which depends on the size and charge of the s-block cation in question. Reaction of the dicopper(I) double-stranded helicate with Ba(2+) shows that the dinuclear structure still remains intact but the pitch length is significantly increased.

Crystal structures of two mononuclear complexes of terbium(III) nitrate with the tripodal alcohol 1,1,1-tris-(hy-droxy-meth-yl)propane.

PubMed

Gregório, Thaiane; Giese, Siddhartha O K; Nunes, Giovana G; Soares, Jaísa F; Hughes, David L

2017-02-01

Two new mononuclear cationic complexes in which the Tb III ion is bis-chelated by the tripodal alcohol 1,1,1-tris-(hy-droxy-meth-yl)propane (H 3 L Et , C 6 H 14 O 3 ) were prepared from Tb(NO 3 ) 3 ·5H 2 O and had their crystal and mol-ecular structures solved by single-crystal X-ray diffraction analysis after data collection at 100 K. Both products were isolated in reasonable yields from the same reaction mixture by using different crystallization conditions. The higher-symmetry complex dinitratobis[1,1,1-tris-(hy-droxy-meth-yl)propane]-terbium(III) nitrate di-meth-oxy-ethane hemisolvate, [Tb(NO 3 ) 2 (H 3 L Et ) 2 ]NO 3 ·0.5C 4 H 10 O 2 , 1 , in which the lanthanide ion is 10-coordinate and adopts an s -bicapped square-anti-prismatic coordination geometry, contains two bidentate nitrate ions bound to the metal atom; another nitrate ion functions as a counter-ion and a half-mol-ecule of di-meth-oxy-ethane (completed by a crystallographic twofold rotation axis) is also present. In product aqua-nitratobis[1,1,1-tris-(hy-droxy-meth-yl)propane]-terbium(III) dinitrate, [Tb(NO 3 )(H 3 L Et ) 2 (H 2 O)](NO 3 ) 2 , 2 , one bidentate nitrate ion and one water mol-ecule are bound to the nine-coordinate terbium(III) centre, while two free nitrate ions contribute to charge balance outside the tricapped trigonal-prismatic coordination polyhedron. No free water mol-ecule was found in either of the crystal structures and, only in the case of 1 , di-meth-oxy-ethane acts as a crystallizing solvent. In both mol-ecular structures, the two tripodal ligands are bent to one side of the coordination sphere, leaving room for the anionic and water ligands. In complex 2 , the methyl group of one of the H 3 L Et ligands is disordered over two alternative orientations. Strong hydrogen bonds, both intra- and inter-molecular, are found in the crystal structures due to the number of different donor and acceptor groups present.

New water soluble heterometallic complex showing unpredicted coordination modes of EDTA

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

Mudsainiyan, R.K., E-mail: mudsainiyanrk@gmail.com; Jassal, A.K.; Chawla, S.K., E-mail: sukhvinder.k.chawla@gmail.com

2015-10-15

A mesoporous 3D polymeric complex (I) having formula ([Zr(IV)O-μ{sup 3}-(EDTA)Fe(III)OH]·H{sub 2}O){sub n} has been crystallized and characterized by various techniques. Single-crystal X-ray diffraction analysis revealed that complex (I) crystallized in chiral monoclinic space group Cc (space group no. 9) with unexpected coordination modes of EDTA and mixture of two transition metal ions. In this complex, the coordination number of Zr(IV) ion is seven where four carboxylate oxygen atoms, two nitrogen atoms, one oxide atom are coordinating with Zr(IV). Fe(III) is four coordinated and its coordination environment is composed of three different carboxylic oxygen atoms from three different EDTA and onemore » oxygen atom of –OH group. The structure consists of 4-c and 16-c (2-nodal) net with new topology and point symbol for net is (3{sup 36}·4{sup 54}·5{sup 30})·(3{sup 6}). TGA study and XRPD pattern showed that the coordination polymer is quite stable even after losing water molecule and –OH ion. Quenching behavior in fluorescence of ligand is observed by complexation with transition metal ions is due to n–π⁎ transition. The SEM micrograph shows the morphology of complex (I) exhibits spherical shape with size ranging from 50 to 280 nm. The minimum N{sub 2} (S{sub BET}=8.7693 m{sup 2}/g) and a maximum amount of H{sub 2} (high surface area=1044.86 m{sup 2}/g (STP)) could be adsorbed at 77 K. From DLS study, zeta potential is calculated i.e. −7.94 shows the negative charges on the surface of complex. Hirshfeld surface analysis and fingerprint plots revealed influence of weak or non bonding interactions in crystal packing of complex. - Graphical abstract: The complex (I) crystallized with unexpected coordination modes of EDTA having 4-c, 16-c net with new topology and point symbol is (3{sup 36}·4{sup 54}·5{sup 30})·(3{sup 6}). TGA study and XRPD pattern proved its stability with high preference of H{sub 2} uptake by complex. - Highlights: • 3D complex having unexpected coordination modes of EDTA with Zr(IV) and Fe(III). • The structure consists of 4-c and 16-c (2-nodal) net with new topology. • Reasonable S{sub BET} (8.7693 m{sup 2}/g) but high H{sub 2} uptake (1044.86 m{sup 2}/g) due to limited pore size. • Quenching behavior due to n–π⁎ transition by complexation with transition metal ions. • From DLS study, zeta potential value is −7.94.« less

A lead (II) 3D coordination polymer based on a marine cyclic peptide motif.

PubMed

Chakraborty, Subrata; Tyagi, Pooja; Tai, Dar-Fu; Lee, Gene-Hsiang; Peng, Shie-Ming

2013-04-26

The crystal structure of a naturally occurring cyclic tetrapeptide cyclo(Gly-L-Ser-L-Pro-L-Glu) [cyclo(GSPE)] was obtained. The conformation of synthesized cyclo(GSPE) fixes the coordination to lead ion in a 1:1 ratio. This cyclo(GSPE)-Pb complex was constructed as an asymmetric 3D network in the crystalline state. The polymerization of a heavy metal ion with a rigid asymmetric cyclic tetrapeptide represents the first example of a new class of macrocyclic complexes.

Bromidotetra-kis-(2-ethyl-1H-imidazole-κN (3))copper(II) bromide.

PubMed

Godlewska, Sylwia; Kelm, Harald; Krüger, Hans-Jörg; Dołęga, Anna

2012-12-01

The Cu(II) ion in the title mol-ecular salt, [CuBr(C5H8N2)4]Br, is coordinated in a square-pyramidal geometry by four N atoms of imidazole ligands and one bromide anion in the apical position. In the crystal, the ions are linked by N-H⋯Br hydrogen bonds involving both the coordinating and the free bromide species as acceptors. A C-H⋯Br inter-action is also observed. Overall, a three-dimensional network results.

Series of coordination polymers based on 4-(5-sulfo-quinolin-8-yloxy) phthalate and bipyridinyl coligands: Structure diversity and properties

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

Feng, Xun; Liu, Jing; College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022

2015-10-15

Reactions between later metal salts and conjugational N-hetrocyclic sulfonate/ carboxylic acid under the presence of bipyridyl auxiliary ligands afforded a series of manganese, nickel, zinc, silver, cadmium coordination polymers bearing with phenyl pendant arm attached to quinoline skeletons, and they have been characterized by elements analysis, thermogravimetry, infrared spectroscopy and single-crystal X-ray diffraction studying. The series of polymers show interesting structural diversity in coordination environment, dimensions and topologies. They are all built from 2-D networks constructed from metal cluster through sulfonate or carboxylate groups, as the secondary building unit (SBU). The thermalgravimetric analyses show that they display framework stabilities inmore » solid state. Variable-temperature magnetic susceptibility studies reveal the existence of antiferromagnetic interactions between adjacent Mn (II) ions in 1, and ferromagnetic interactions between Ni(II) ions for 2, respectively. The photo-luminescence properties of 3-5 have also been investigated systemically. - Highlights: • A series of coordination polymers based on later transition metal ions have been obtained. • They contain conjugational N-hetrocyclic sulfonate-carboxylic acid and bipyridyl auxiliary ligands. • They have been characterized systemically. • They exhibit structure diversity and interesting properties.« less

Structure of high alumina content Al2O3-SiO2 composition glasses.

PubMed

Weber, Richard; Sen, Sabyasachi; Youngman, Randall E; Hart, Robert T; Benmore, Chris J

2008-12-25

The structure of binary aluminosilicate glasses containing 60-67 mol % Al2O3 were investigated using high-resolution 27Al NMR and X-ray and neutron diffraction. The glasses were made by aerodynamic levitation of molten oxides. The 67% alumina composition required a cooling rate of approximately 1600 degrees C s(1-) to form glass from submillimeter sized samples. NMR results show that the glasses contain aluminum in 4-, 5-, and 6-fold coordination in the approximate ratio 4:5:1. The average Al coordination increases from 4.57 to 4.73 as the fraction of octahedral Al increases with alumina content. The diffraction results on the 67% composition are consistent with a disordered Al framework with Al ions in a range of coordination environments that are substantially different from those found in the equilibrium crystalline phases. Analysis of the neutron and X-ray structure factors yields an average bond angle of 125 +/- 4 degrees between an Al ion and the adjoining cation via a bridging oxygen. We propose that the structure of the glass is a "transition state" between the alumina-rich liquid and the equilibrium mullite phase that are dominated by 4- and 6-coordinated aluminum ions, respectively.

Infrared Multiple-Photon Dissociation spectroscopy of group II metal complexes with salicylate

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

Ryan P. Dain; Gary Gresham; Gary S. Groenewold

2011-07-01

Ion-trap tandem mass spectrometry with collision-induced dissociation, and the combination of infrared multiple-photon dissociation (IRMPD) spectroscopy and density functional theory (DFT) calculations were used to characterize singly-charged, 1:1 complexes of Ca2+, Sr2+ and Ba2+ with salicylate. For each metal-salicylate complex, the CID pathways are: (a) elimination of CO2 and (b) formation of [MOH]+ where M=Ca2+, Sr2+ or Ba2+. DFT calculations predict three minima for the cation-salicylate complexes which differ in the mode of metal binding. In the first, the metal ion is coordinated by O atoms of the (neutral) phenol and carboxylate groups of salicylate. In the second, the cationmore » is coordinated by phenoxide and (neutral) carboxylic acid groups. The third mode involves coordination by the carboxylate group alone. The infrared spectrum for the metal-salicylate complexes contains a number of absorptions between 1000 – 1650 cm-1, and the best correlation between theoretical and experimental spectra for the structure that features coordination of the metal ion by phenoxide and the carbonyl group of the carboxylic acid group, consistent with calculated energies for the respective species.« less

Infrared multiple-photon dissociation spectroscopy of group II metal complexes with salicylate.

PubMed

Dain, Ryan P; Gresham, Gary; Groenewold, Gary S; Steill, Jeffrey D; Oomens, Jos; van Stipdonk, Michael J

2011-07-15

Ion trap tandem mass spectrometry with collision-induced dissociation, and the combination of infrared multiple-photon dissociation (IRMPD) spectroscopy and density functional theory (DFT) calculations, were used to characterize singly charged, 1:1 complexes of Ca(2+), Sr(2+) and Ba(2+) with salicylate. For each metal-salicylate complex, the CID pathways are: (a) elimination of CO(2) and (b) formation of [MOH](+) where M = Ca(2+), Sr(2+) or Ba(2+). DFT calculations predict three minima for the cation-salicylate complexes which differ in the mode of metal binding. In the first, the metal ion is coordinated by O atoms of the (neutral) phenol and carboxylate groups of salicylate. In the second, the cation is coordinated by phenoxide and (neutral) carboxylic acid groups. The third mode involves coordination by the carboxylate group alone. The infrared spectrum for the metal-salicylate complexes contains a number of absorptions between 1000 and 1650 cm(-1), and the best correlation between theoretical and experimental spectra is found for the structure that features coordination of the metal ion by phenoxide and the carbonyl O of the carboxylic acid group, consistent with the calculated energies for the respective species. Copyright © 2011 John Wiley & Sons, Ltd.

Oblique Alfvén instabilities driven by compensated currents

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

Malovichko, P.; Voitenko, Y.; De Keyser, J., E-mail: voitenko@oma.be

2014-01-10

Compensated-current systems created by energetic ion beams are widespread in space and astrophysical plasmas. The well-known examples are foreshock regions in the solar wind and around supernova remnants. We found a new oblique Alfvénic instability driven by compensated currents flowing along the background magnetic field. Because of the vastly different electron and ion gyroradii, oblique Alfvénic perturbations react differently on the currents carried by the hot ion beams and the return electron currents. Ultimately, this difference leads to a non-resonant aperiodic instability at perpendicular wavelengths close to the beam ion gyroradius. The instability growth rate increases with increasing beam currentmore » and temperature. In the solar wind upstream of Earth's bow shock, the instability growth time can drop below 10 proton cyclotron periods. Our results suggest that this instability can contribute to the turbulence and ion acceleration in space and astrophysical foreshocks.« less

High frequency fishbone driven by passing energetic ions in tokamak plasmas

NASA Astrophysics Data System (ADS)

Wang, Feng; Yu, L. M.; Fu, G. Y.; Shen, Wei

2017-05-01

High frequency fishbone instability driven by passing energetic ions was first reported in the Princeton beta experiment with tangential neutral-beam-injection (Heidbrink et al 1986 Phys. Rev. Lett. 57 835-8). It could play an important role for ITER-like burning plasmas, where α particles are mostly passing particles. In this work, a generalized energetic ion distribution function and finite drift orbit width effect are considered to improve the theoretical model for passing particle driving fishbone instability. For purely passing energetic ions with zero drift orbit width, the kinetic energy δ {{W}k} is derived analytically. The derived analytic expression is more accurate as compared to the result of previous work (Wang 2001 Phys. Rev. Lett. 86 5286-8). For a generalized energetic ion distribution function, the fishbone dispersion relation is derived and is solved numerically. Numerical results show that broad and off-axis beam density profiles can significantly increase the beam ion beta threshold {βc} for instability and decrease mode frequency.

High frequency fishbone driven by passing energetic ions in tokamak plasmas

DOE PAGES

Wang, Feng; Yu, L. M.; Fu, G. Y.; ...

2017-03-22

High frequency fishbone instability driven by passing energetic ions was first reported in the Princeton beta experiment with tangential neutral-beam-injection (Heidbrink et al 1986 Phys. Rev. Lett. 57 835–8). It could play an important role for ITER-like burning plasmas, where α particles are mostly passing particles. In this work, a generalized energetic ion distribution function and finite drift orbit width effect are considered to improve the theoretical model for passing particle driving fishbone instability. For purely passing energetic ions with zero drift orbit width, the kinetic energymore » $$\\delta {{W}_{k}}$$ is derived analytically. The derived analytic expression is more accurate as compared to the result of previous work. For a generalized energetic ion distribution function, the fishbone dispersion relation is derived and is solved numerically. As a result, numerical results show that broad and off-axis beam density profiles can significantly increase the beam ion beta threshold $${{\\beta}_{c}}$$ for instability and decrease mode frequency.« less

Ion species stratification within strong shocks in two-ion plasmas

DOE PAGES

Keenan, Brett D.; Simakov, Andrei N.; Taitano, William T.; ...

2018-03-01

We report strong collisional shocks in multi-ion plasmas are featured in many environments, with Inertial Confinement Fusion (ICF) experiments being one prominent example. Recent work [Keenan et al., Phys. Rev. E 96, 053203 (2017)] answered in detail a number of outstanding questions concerning the kinetic structure of steady-state, planar plasma shocks, e.g., the shock width scaling by the Mach number, M. However, it did not discuss shock-driven ion-species stratification (e.g., relative concentration modification and temperature separation). These are important effects since many recent ICF experiments have evaded explanation by standard, single-fluid, radiation-hydrodynamic (rad-hydro) numerical simulations, and shock-driven fuel stratification likelymore » contributes to this discrepancy. Employing the state-of-the-art Vlasov-Fokker-Planck code, iFP, along with multi-ion hydro simulations and semi-analytics, we quantify the ion stratification by planar shocks with the arbitrary Mach number and the relative species concentration for two-ion plasmas in terms of ion mass and charge ratios. In particular, for strong shocks, we find that the structure of the ion temperature separation has a nearly universal character across ion mass and charge ratios. Lastly, we find that the shock fronts are enriched with the lighter ion species and the enrichment scales as M 4 for M»1.« less

Ion species stratification within strong shocks in two-ion plasmas

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

Keenan, Brett D.; Simakov, Andrei N.; Taitano, William T.

We report strong collisional shocks in multi-ion plasmas are featured in many environments, with Inertial Confinement Fusion (ICF) experiments being one prominent example. Recent work [Keenan et al., Phys. Rev. E 96, 053203 (2017)] answered in detail a number of outstanding questions concerning the kinetic structure of steady-state, planar plasma shocks, e.g., the shock width scaling by the Mach number, M. However, it did not discuss shock-driven ion-species stratification (e.g., relative concentration modification and temperature separation). These are important effects since many recent ICF experiments have evaded explanation by standard, single-fluid, radiation-hydrodynamic (rad-hydro) numerical simulations, and shock-driven fuel stratification likelymore » contributes to this discrepancy. Employing the state-of-the-art Vlasov-Fokker-Planck code, iFP, along with multi-ion hydro simulations and semi-analytics, we quantify the ion stratification by planar shocks with the arbitrary Mach number and the relative species concentration for two-ion plasmas in terms of ion mass and charge ratios. In particular, for strong shocks, we find that the structure of the ion temperature separation has a nearly universal character across ion mass and charge ratios. Lastly, we find that the shock fronts are enriched with the lighter ion species and the enrichment scales as M 4 for M»1.« less

Ion species stratification within strong shocks in two-ion plasmas

NASA Astrophysics Data System (ADS)

Keenan, Brett D.; Simakov, Andrei N.; Taitano, William T.; Chacón, Luis

2018-03-01

Strong collisional shocks in multi-ion plasmas are featured in many environments, with Inertial Confinement Fusion (ICF) experiments being one prominent example. Recent work [Keenan et al., Phys. Rev. E 96, 053203 (2017)] answered in detail a number of outstanding questions concerning the kinetic structure of steady-state, planar plasma shocks, e.g., the shock width scaling by the Mach number, M. However, it did not discuss shock-driven ion-species stratification (e.g., relative concentration modification and temperature separation). These are important effects since many recent ICF experiments have evaded explanation by standard, single-fluid, radiation-hydrodynamic (rad-hydro) numerical simulations, and shock-driven fuel stratification likely contributes to this discrepancy. Employing the state-of-the-art Vlasov-Fokker-Planck code, iFP, along with multi-ion hydro simulations and semi-analytics, we quantify the ion stratification by planar shocks with the arbitrary Mach number and the relative species concentration for two-ion plasmas in terms of ion mass and charge ratios. In particular, for strong shocks, we find that the structure of the ion temperature separation has a nearly universal character across ion mass and charge ratios. Additionally, we find that the shock fronts are enriched with the lighter ion species and the enrichment scales as M4 for M ≫ 1.

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

Zhang, Yingjie, E-mail: yzx@ansto.gov.au; Karatchevtseva, Inna; Bhadbhade, Mohan

With the coordination of dimethylformamide (DMF), two new uranium(VI) complexes with either 4-hydroxybenzoic acid (H{sub 2}phb) or terephthalic acid (H{sub 2}tph) have been synthesized under solvothermal conditions and structurally characterized. [(UO{sub 2}){sub 2}(Hphb){sub 2}(phb)(DMF)(H{sub 2}O){sub 3}]·4H{sub 2}O (1) has a dinuclear structure constructed with both pentagonal and hexagonal bipyramidal uranium polyhedra linked through a µ{sub 2}-bridging ligand via both chelating carboxylate arm and alcohol oxygen bonding, first observation of such a coordination mode of 4-hydroxybenzoate for 5 f ions. [(UO{sub 2})(tph)(DMF)] (2) has a three-dimensional (3D) framework built with pentagonal bipyramidal uranium polyhedra linked with µ{sub 4}-terephthalate ligands. The 3Dmore » channeled structure is facilitated by the unique carboxylate bonding with nearly linear C–O–U angles and the coordination of DMF molecules. The presence of phb ligands in different coordination modes, uranyl ions in diverse environments and DMF in complex 1, and tph ligand, DMF and uranyl ion in complex 2 has been confirmed by Raman spectroscopy. In addition, their thermal stability and photoluminescence properties have been investigated. - Graphical abstract: With the coordination of dimethylformamide, two new uranyl complexes with either 4-hydroxybenzoate or terephthalate have been synthesized under solvothermal conditions and structurally characterized. - Highlights: • Solvent facilitates the synthesis of two new uranium(VI) complexes. • A dinuclear complex with both penta- and hexagonal bipyramidal uranium polyhedral. • A unique µ{sub 2}-bridging mode of 4-hydroxybenzoate via alcohol oxygen for 5 f ions. • A 3D framework with uranium polyhedra and µ{sub 4}-terephthalate ligands. • Vibration modes and photoluminescence properties are reported.« less

Ion concentration in micro and nanoscale electrospray emitters.

PubMed

Yuill, Elizabeth M; Baker, Lane A

2018-06-01

Solution-phase ion transport during electrospray has been characterized for nanopipettes, or glass capillaries pulled to nanoscale tip dimensions, and micron-sized electrospray ionization emitters. Direct visualization of charged fluorophores during the electrospray process is used to evaluate impacts of emitter size, ionic strength, analyte size, and pressure-driven flow on heterogeneous ion transport during electrospray. Mass spectrometric measurements of positively- and negatively-charged proteins were taken for micron-sized and nanopipette emitters under low ionic strength conditions to further illustrate a discrepancy in solution-driven transport of charged analytes. A fundamental understanding of analyte electromigration during electrospray, which is not always considered, is expected to provide control over selective analyte depletion and enrichment, and can be harnessed for sample cleanup. Graphical abstract Fluorescence micrographs of ion migration in nanoscale pipettes while solution is electrosprayed.

Stability of coordination compounds of Ni2+ and Co2+ ions with succinic acid anion in water-ethanol solvents

NASA Astrophysics Data System (ADS)

Tukumova, N. V.; Dieu Thuan, Tran Thi; Usacheva, T. R.; Koryshev, N. E.; Sharnin, V. A.

2017-04-01

Stability constants of the coordination compounds of nickel(II) and cobalt(II) ions with succinic acid anion in water-ethanol solvents are determined via potentiometric titration at ionic strength of 0.1 and at T = 298.15 K. It is found that logβ values of monoligand complexes of these ions and succinic acid anions rise along with the content of ethanol in solution ( X EtOH = 0-0.7 mole fractions). Based on an analysis of the thermodynamic characteristics of the solvation of the reagents involved in complex formation, it is found that the increased stability of succinate complexes of nickel(II) and cobalt(II) ions in water-ethanol solvents is mainly determined by the weakening of the solvation of succinic acid anion (Y2-).

Models for the Immediate Environment of Ions in Aqueous Solutions of Neodymium Chloride

NASA Astrophysics Data System (ADS)

Smirnov, P. R.; Grechin, O. V.

2018-01-01

Radial distribution functions of neodymium chloride aqueous solutions in a wide range of concentrations under ambient conditions are calculated from experimental data obtained earlier via X-ray diffraction analysis. Different models of the structural organization of the system are developed. The optimum versions are determined by calculating theoretical functions for each model and comparing their fit to the experimental functions. Such quantitative characteristics of the immediate environment of Nd3+ and Cl- ions as coordination numbers, interparticle distances, and varieties of ion pairs are determined. It is shown that the average number of water molecules in the first coordination sphere of the cation falls from 9 to 6.2 as the concentration rises. The structure of the systems over the whole range of concentrations is determined by ion associates of the noncontact type.

Investigation of rubidium(I) ion solvation in liquid ammonia using QMCF-MD simulation and NBO analysis of first solvation shell structure.

PubMed

Hidayat, Yuniawan; Armunanto, Ria; Pranowo, Harno Dwi

2018-04-27

Rb(I) ion solvation in liquid ammonia has been studied by an ab initio quantum mechanical charge field molecular dynamics simulation, and the first solvation shell structure has been analyzed using natural bond orbital. The simulation was performed for an ion and 593 ammonia molecules in a box with a length of 29.03 Å corresponding to a liquid ammonia density of 0.69 g/mL at 235.16 K. The quantum mechanical calculation was carried out for atomic interactions in the radius of 6.4 Å from the ion using LANL2DZ ECP and DZP (Dunning) basis sets for Rb(I) ion and ammonia respectively. The trajectories of the simulation were analyzed in terms of radial, angular, and coordination number distribution functions, vibration, and mean residence time (MRT). Two solvation shell regions are observed for the Rb(I)-N as well as the Rb(I)-H. The maximum distance of Rb(I)-N in the first solvation shell is in accordance with experimental data where a coordination number of 8 is favorable. A non-single coordination number of the first and second shell indicates dynamic solvation structure. It is confirmed by frequent exchange ligand processes observed within a simulation time of 15 ps. The low stabilization energy of donor acceptor ion-ligand interaction with a small Wiberg bond index affirms that the Rb(I)-NH 3 interaction is weak electrostatically.

Coordination chemistry of vitamin C. Part I. Interaction of L-ascorbic acid with alkaline earth metal ions in the crystalline solid and aqueous solution.

PubMed

Tajmir-Riahi, H A

1990-10-01

The interaction of L-ascorbic acid with alkaline earth metal ions has been investigated in aqueous solution at pH 6-7. The solid salts of the type Mg(L-ascorbate)2.4H2O, Ca(L-ascorbate)2.2H2O, Sr(L-ascorbate)2.2H2O and Ba(L-ascorbate)2.2H2O were isolated and characterized by means of 13C NMR and FT-IR spectroscopy. Spectroscopic and other evidence suggested that in aqueous solution, the binding of the alkaline earth metal ions is through the O-3 atom of the ascorbate anion, while in the solid state the binding of the Mg(II) is different from those of the other alkaline earth metal ion salts. The Mg(II) ion binds to the O-3, O-1 atom of the two ascorbate anions and to two H2O molecules, while the eight-coordination around the Ca(II), Sr(II), and Ba(II) ions would be completed by the coordination of three acid anions, through O-5, O-6 of the first, O-3, O-5, O-6 of the second and O-1 of the third anion as well as to two H2O molecules. The structural properties of the alkaline earth metal-ascorbate salts are different in the solid and aqueous solution.

Syntheses, crystal structures and spectroscopic properties of copper(II)-tetracyanometallate(II) complexes with nicotinamide and isonicotinamide ligands

NASA Astrophysics Data System (ADS)

Sayın, Elvan; Kürkçüoğlu, Güneş Süheyla; Yeşilel, Okan Zafer; Hökelek, Tuncer

2015-09-01

Four new one dimensional (1D) cyanide complexes, namely {[Cu(NH3)4(μ-na)][M‧(CN)4]}n and {[Cu(NH3)2(ina)2M‧(μ-CN)2(CN)2]}n (M‧(II) = Pd (1 and 3) or Pt (2 and 4), na:nicotinamide and ina:isonicotinamide) have been synthesized and characterized by elemental, spectral (FT-IR and Raman), and thermal (TG, DTG and DTA) analyses. The crystal structures of complexes 1-3 have been determined by single crystal X-ray diffraction technique. In complexes 1 and 2, na ligand is coordinated to the adjacent Cu(II) ions as a bridging ligand, giving rise to 1D linear cationic chain and the [M‧(CN)4]2- anionic complex acts as a counter ion. Complexes 3 and 4 are also 1D linear chain in which two cyanide ligands bridged neighboring M‧(II) and Cu(II) ions, while ina ligand is coordinated Cu(II) ion through nitrogen atom of pyridine ring. In the complexes, the Cu(II) ions adopt distorted octahedral geometries, while M‧(II) ions are four coordinated with four carbon atoms from cyanide ligands in square-planar geometries. The adjacent chains are further stacked through intermolecular hydrogen bond, Nsbnd Hṡṡṡπ, Csbnd H⋯M‧ and M‧⋯π interactions to form 3D supramolecular networks. Vibration assignments are given for all the observed bands. In addition, thermal stabilities of the compounds are also discussed.

3D visualization of solar wind ion data from the Chang'E-1 exploration

NASA Astrophysics Data System (ADS)

Zhang, Tian; Sun, Yankui; Tang, Zesheng

2011-10-01

Chang'E-1 (abbreviation CE-1), China's first Moon-orbiting spacecraft launched in 2007, carried equipment called the Solar Wind Ion Detector (abbreviation SWID), which sent back tens of gigabytes of solar wind ion differential number flux data. These data are essential for furthering our understanding of the cislunar space environment. However, to fully comprehend and analyze these data presents considerable difficulties, not only because of their huge size (57 GB), but also because of their complexity. Therefore, a new 3D visualization method is developed to give a more intuitive representation than traditional 1D and 2D visualizations, and in particular to offer a better indication of the direction of the incident ion differential number flux and the relative spatial position of CE-1 with respect to the Sun, the Earth, and the Moon. First, a coordinate system named Selenocentric Solar Ecliptic (SSE) which is more suitable for our goal is chosen, and solar wind ion differential number flux vectors in SSE are calculated from Geocentric Solar Ecliptic System (GSE) and Moon Center Coordinate (MCC) coordinates of the spacecraft, and then the ion differential number flux distribution in SSE is visualized in 3D space. This visualization method is integrated into an interactive visualization analysis software tool named vtSWIDs, developed in MATLAB, which enables researchers to browse through numerous records and manipulate the visualization results in real time. The tool also provides some useful statistical analysis functions, and can be easily expanded.

Alkali-Resistant Mechanism of a Hollandite DeNOx Catalyst.

PubMed

Hu, Pingping; Huang, Zhiwei; Gu, Xiao; Xu, Fei; Gao, Jiayi; Wang, Yue; Chen, Yaxin; Tang, Xingfu

2015-06-02

A thorough understanding of the deactivation mechanism by alkalis is of great importance for rationally designing improved alkali-resistant deNOx catalysts, but a traditional ion-exchange mechanism cannot often accurately describe the nature of the deactivation, thus hampering the development of superior catalysts. Here, we establish a new exchange-coordination mechanism on the basis of the exhaustive study on the strong alkali resistance of a hollandite manganese oxide (HMO) catalyst. A combination of isothermal adsorption measurements of ammonia with X-ray absorption near-edge structure spectra and X-ray photoelectron spectra reveals that alkali metal ions first react with protons from Brønsted acid sites of HMO via the ion exchange. Synchrotron X-ray diffraction patterns and extended X-ray absorption fine structure spectra coupled with theoretical calculations demonstrate that the exchanged alkali metal ions are subsequently stabilized at size-suitable cavities in the HMO pores via a coordination model with an energy savings. This exchange-coordination mechanism not only gives a wholly convincing explanation for the intrinsic nature of the deactivation of the reported catalysts by alkalis but also provides a strategy for rationally designing improved alkali-resistant deNOx catalysts in general.

One dimensional coordination polymers: Synthesis, crystal structures and spectroscopic properties

NASA Astrophysics Data System (ADS)

Karaağaç, Dursun; Kürkçüoğlu, Güneş Süheyla; Şenyel, Mustafa; Şahin, Onur

2016-11-01

Two new one dimensional (1D) cyanide complexes, namely [M(4-aepy)2(H2O)2][Pt(CN)4], (4-aepy = 4-(2-aminoethyl)pyridine M = Cu(II) (1) or Zn(II) (2)), have been synthesized and characterized by vibrational (FT-IR and Raman) spectroscopy, single crystal X-ray diffraction, thermal and elemental analyses techniques. The crystallographic analyses reveal that 1 and 2 are isomorphous and isostructural, and crystallize in the monoclinic system and C2 space group. The Pt(II) ions are coordinated by four cyanide-carbon atoms in the square-planar geometry and the [Pt(CN)4]2- ions act as a counter ion. The M(II) ions display an N4O2 coordination sphere with a distorted octahedral geometry, the nitrogen donors belonging to four molecules of the organic 4-aepy that act as unidentate ligands and two oxygen atoms from aqua ligands. The crystal structures of 1 and 2 are similar each other and linked via intermolecular hydrogen bonding, Pt⋯π interactions to form 3D supramolecular network. Vibration assignments of all the observed bands are given and the spectral features also supported to the crystal structures of the complexes.

Effects of MHD instabilities on neutral beam current drive

NASA Astrophysics Data System (ADS)

Podestà, M.; Gorelenkova, M.; Darrow, D. S.; Fredrickson, E. D.; Gerhardt, S. P.; White, R. B.

2015-05-01

Neutral beam injection (NBI) is one of the primary tools foreseen for heating, current drive (CD) and q-profile control in future fusion reactors such as ITER and a Fusion Nuclear Science Facility. However, fast ions from NBI may also provide the drive for energetic particle-driven instabilities (e.g. Alfvénic modes (AEs)), which in turn redistribute fast ions in both space and energy, thus hampering the control capabilities and overall efficiency of NB-driven current. Based on experiments on the NSTX tokamak (M. Ono et al 2000 Nucl. Fusion 40 557), the effects of AEs and other low-frequency magneto-hydrodynamic instabilities on NB-CD efficiency are investigated. A new fast ion transport model, which accounts for particle transport in phase space as required for resonant AE perturbations, is utilized to obtain consistent simulations of NB-CD through the tokamak transport code TRANSP. It is found that instabilities do indeed reduce the NB-driven current density over most of the plasma radius by up to ∼50%. Moreover, the details of the current profile evolution are sensitive to the specific model used to mimic the interaction between NB ions and instabilities. Implications for fast ion transport modeling in integrated tokamak simulations are briefly discussed.

Effects of MHD instabilities on neutral beam current drive

DOE PAGES

Podestà, M.; Gorelenkova, M.; Darrow, D. S.; ...

2015-04-17

One of the primary tools foreseen for heating, current drive (CD) and q-profile control in future fusion reactors such as ITER and a Fusion Nuclear Science Facility is the neutral beam injection (NBI). However, fast ions from NBI may also provide the drive for energetic particle-driven instabilities (e.g. Alfvénic modes (AEs)), which in turn redistribute fast ions in both space and energy, thus hampering the control capabilities and overall efficiency of NB-driven current. Based on experiments on the NSTX tokamak (M. Ono et al 2000 Nucl. Fusion 40 557), the effects of AEs and other low-frequency magneto-hydrodynamic instabilities on NB-CDmore » efficiency are investigated. When looking at the new fast ion transport model, which accounts for particle transport in phase space as required for resonant AE perturbations, is utilized to obtain consistent simulations of NB-CD through the tokamak transport code TRANSP. It is found that instabilities do indeed reduce the NB-driven current density over most of the plasma radius by up to ~50%. Moreover, the details of the current profile evolution are sensitive to the specific model used to mimic the interaction between NB ions and instabilities. Finally, implications for fast ion transport modeling in integrated tokamak simulations are briefly discussed.« less

Non-traditional Oxidants in Preparative Coordination Chemistry

NASA Astrophysics Data System (ADS)

Kukushkin, Vadim Yu; Kukushkin, Yurii N.

1986-10-01

The application of nitrosonium and arenediazonium salts, carbenium, silver(I), and mercury(II) ions, protic acids, and amine oxides as oxidants in preparative coordination chemistry is examined. Specific examples illustrate which problems in the field of the synthesis and reactions of coordination compounds can be solved with the aid of these oxidants. The bibliography includes 158 references.

One-Pot Synthesis of Co-Based Coordination Polymer Nanowire for Li-Ion Batteries with Great Capacity and Stable Cycling Stability

NASA Astrophysics Data System (ADS)

Wang, Peng; Lou, Xiaobing; Li, Chao; Hu, Xiaoshi; Yang, Qi; Hu, Bingwen

2018-06-01

Nanowire coordination polymer cobalt-terephthalonitrile (Co-BDCN) was successfully synthesized using a simple solvothermal method and applied as anode material for lithium-ion batteries (LIBs). A reversible capacity of 1132 mAh g-1 was retained after 100 cycles at a rate of 100 mA g-1, which should be one of the best LIBs performances among metal organic frameworks and coordination polymers-based anode materials at such a rate. On the basis of the comprehensive structural and morphology characterizations including fourier transform infrared spectroscopy, 1H NMR, 13C NMR, and scanning electron microscopy, we demonstrated that the great electrochemical performance of the as-synthesized Co-BDCN coordination polymer can be attributed to the synergistic effect of metal centers and organic ligands, as well as the stability of the nanowire morphology during cycling.[Figure not available: see fulltext.

Synthesis and characterization of a metal complex containing naringin and Cu, and its antioxidant, antimicrobial, antiinflammatory and tumor cell cytotoxicity.

PubMed

Pereira, Regina M S; Andrades, Norma E D; Paulino, Niraldo; Sawaya, Alexandra C H F; Eberlin, Marcos N; Marcucci, Maria C; Favero, Giovani Marino; Novak, Estela Maria; Bydlowski, Sérgio Paulo

2007-07-09

The antioxidant activity of flavonoids is believed to increase when they are coordinated with transition metal ions. However, the literature on this subject is contradictory and the outcome seems to largely depend on the experimental conditions. In order to understand the contribution of the metal coordination and the type of interaction between a flavonoid and the metal ion, in this study a new metal complex of Cu (II) with naringin was synthesized and characterized by FT-IR, UV-VIS, mass spectrometry (ESI-MS/MS), elemental analysis and 1H-NMR. The results of these analyses indicate that the complex has a Cu (II) ion coordinated via positions 4 and 5 of the flavonoid. The antioxidant, anti-inflammatory and antimicrobial activities of this complex were studied and compared with the activity of free naringin. The Naringin-Cu (II) complex 1 showed higher antioxidant, anti-inflammatory and tumor cell cytotoxicity activities than free naringin without reducing cell viability.

catena-Poly[[[triaqua­sulfatozinc(II)]-μ-3,3′-bis­(3-pyrid­yl)-1,1′-(m-phenyl­ene)diurea] methanol solvate monohydrate

PubMed Central

Adarsh, N. N.; Dastidar, Parthasarathi

2010-01-01

In the title coordination polymer, {[Zn(SO4)(C18H16N6O2)(H2O)3]·CH3OH·H2O}n, the Zn2+ ion adopts a slightly distorted cis-ZnN2O4 octa­hedral geometry arising from three coordinated water mol­ecules, one sulfate ion and two bridging 3,3′-bis­(3-pyrid­yl)-1,1′-(m-phenyl­ene)diurea (bpmpbu) ligands. The dihedral angles between the central benzene ring and two terminal pyridine rings of the bpmbpu mol­ecule are 10.58 (17) and 34.63 (16)°. In the crystal, the ligands bridge the ZnII ions, thus generating a one-dimensional zigzag coordination polymer propagating in [010]. The crystal structure features extensive N—H⋯O and O—H⋯O hydrogen-bonding inter­actions. PMID:21580512

Building thiol and metal-thiolate functions into coordination nets: Clues from a simple molecule

NASA Astrophysics Data System (ADS)

He, Jun; Yang, Chen; Xu, Zhengtao; Zeller, Matthias; Hunter, Allen D.; Lin, Jianhua

2009-07-01

The simple and easy-to-prepare bifunctional molecule 2,5-dimercapto-1,4-benzenedicarboxylic acid (H 4DMBD) interacts with the increasingly harder metal ions of Cu +, Pb 2+ and Eu 3+ to form the coordination networks of Cu 6(DMBD) 3(en) 4(Hen) 6 ( 1), Pb 2(DMBD)(en) 2 ( 2) and Eu 2(H 2DMBD) 3(DEF) 4 ( 3), where the carboxyl and thiol groups bind with distinct preference to the hard and soft metal ions, respectively. Notably, 1 features uncoordinated carboxylate groups and Cu 3 cluster units integrated via the thiolate groups into an extended network with significant interaction between the metal centers and the organic molecules; 2 features a 2D coordination net based on the mercapto and carboxylic groups all bonded to the Pb 2+ ions; 3 features free-standing thiol groups inside the channels of a metal-carboxylate-based network. This study illustrates the rich solid state structural features and potential functions offered by the carboxyl-thiol combination.

Synthesis and Characterization of the Actinium Aquo Ion

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

Ferrier, Maryline G.; Stein, Benjamin W.; Batista, Enrique R.

Metal aquo ions occupy central roles in all equilibria that define metal complexation in natural environments. These complexes are used to establish thermodynamic metrics (i.e., stability constants) for predicting metal binding, which are essential for defining critical parameters associated with aqueous speciation, metal chelation, in vivo transport, and so on. As such, establishing the fundamental chemistry of the actinium(III) aquo ion (Ac-aquo ion, Ac(H 2O) x 3+) is critical for current efforts to develop 225Ac [t 1/2 = 10.0(1) d] as a targeted anticancer therapeutic agent. However, given the limited amount of actinium available for study and its high radioactivity,more » many aspects of actinium chemistry remain poorly defined. We overcame these challenges using the longer-lived 227Ac [t 1/2 = 21.772(3) y] isotope and report the first characterization of this fundamentally important Ac-aquo coordination complex. Our X-ray absorption fine structure study revealed 10.9 ± 0.5 water molecules directly coordinated to the Ac III cation with an Ac–O H2O distance of 2.63(1) Å. This experimentally determined distance was consistent with molecular dynamics density functional theory results that showed (over the course of 8 ps) that Ac III was coordinated by 9 water molecules with Ac–O H2O distances ranging from 2.61 to 2.76 Å. Lastly, the data is presented in the context of other actinide(III) and lanthanide(III) aquo ions characterized by XAFS and highlights the uniqueness of the large Ac III coordination numbers and long Ac–O H2O bond distances.« less

Synthesis and Characterization of the Actinium Aquo Ion

DOE PAGES

Ferrier, Maryline G.; Stein, Benjamin W.; Batista, Enrique R.; ...

2017-02-01

Metal aquo ions occupy central roles in all equilibria that define metal complexation in natural environments. These complexes are used to establish thermodynamic metrics (i.e., stability constants) for predicting metal binding, which are essential for defining critical parameters associated with aqueous speciation, metal chelation, in vivo transport, and so on. As such, establishing the fundamental chemistry of the actinium(III) aquo ion (Ac-aquo ion, Ac(H 2O) x 3+) is critical for current efforts to develop 225Ac [t 1/2 = 10.0(1) d] as a targeted anticancer therapeutic agent. However, given the limited amount of actinium available for study and its high radioactivity,more » many aspects of actinium chemistry remain poorly defined. We overcame these challenges using the longer-lived 227Ac [t 1/2 = 21.772(3) y] isotope and report the first characterization of this fundamentally important Ac-aquo coordination complex. Our X-ray absorption fine structure study revealed 10.9 ± 0.5 water molecules directly coordinated to the Ac III cation with an Ac–O H2O distance of 2.63(1) Å. This experimentally determined distance was consistent with molecular dynamics density functional theory results that showed (over the course of 8 ps) that Ac III was coordinated by 9 water molecules with Ac–O H2O distances ranging from 2.61 to 2.76 Å. Lastly, the data is presented in the context of other actinide(III) and lanthanide(III) aquo ions characterized by XAFS and highlights the uniqueness of the large Ac III coordination numbers and long Ac–O H2O bond distances.« less

Mean bond-length variations in crystals for ions bonded to oxygen

PubMed Central

2017-01-01

Variations in mean bond length are examined in oxide and oxysalt crystals for 55 cation configurations bonded to O2−. Stepwise multiple regression analysis shows that mean bond length is correlated to bond-length distortion in 42 ion configurations at the 95% confidence level, with a mean coefficient of determination (〈R 2〉) of 0.35. Previously published correlations between mean bond length and mean coordination number of the bonded anions are found not to be of general applicability to inorganic oxide and oxysalt structures. For two of 11 ions tested for the 95% confidence level, mean bond lengths predicted using a fixed radius for O2− are significantly more accurate as those predicted using an O2− radius dependent on coordination number, and are statistically identical otherwise. As a result, the currently accepted ionic radii for O2− in different coordinations are not justified by experimental data. Previously reported correlation between mean bond length and the mean electronegativity of the cations bonded to the oxygen atoms of the coordination polyhedron is shown to be statistically insignificant; similar results are obtained with regard to ionization energy. It is shown that a priori bond lengths calculated for many ion configurations in a single structure-type leads to a high correlation between a priori and observed mean bond lengths, but a priori bond lengths calculated for a single ion configuration in many different structure-types leads to negligible correlation between a priori and observed mean bond lengths. This indicates that structure type has a major effect on mean bond length, the magnitude of which goes beyond that of the other variables analyzed here.

Modeling of ion transport through a porous separator in vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Zhou, X. L.; Zhao, T. S.; An, L.; Zeng, Y. K.; Wei, L.

2016-09-01

In this work, we develop a two-dimensional, transient model to investigate the mechanisms of ion-transport through a porous separator in VRFBs and their effects on battery performance. Commercial-available separators with pore sizes of around 45 nm are particularly investigated and effects of key separator design parameters and operation modes are explored. We reveal that: i) the transport mechanism of vanadium-ion crossover through available separators is predominated by convection; ii) reducing the pore size below 15 nm effectively minimizes the convection-driven vanadium-ion crossover, while further reduction in migration- and diffusion-driven vanadium-ion crossover can be achieved only when the pore size is reduced to the level close to the sizes of vanadium ions; and iii) operation modes that can affect the pressure at the separator/electrode interface, such as the electrolyte flow rate, exert a significant influence on the vanadium-ion crossover rate through the available separators, indicating that it is critically important to equalize the pressure on each half-cell of a power pack in practical applications.

Enhancement of negative hydrogen ion production in an electron cyclotron resonance source

NASA Astrophysics Data System (ADS)

Dugar-Zhabon, V. D.; Murillo, M. T.; Karyaka, V. I.

2013-07-01

In this paper, we present a method for improving the negative hydrogen ion yield in the electron cyclotron resonance source with driven plasma rings where the negative ion production is realized in two stages. First, the hydrogen and deuterium molecules are excited in collisions with plasma electrons to high-laying Rydberg and high vibration levels in the plasma volume. The second stage leads to negative ion production through the process of repulsive attachment of low-energy electrons by the excited molecules. The low-energy electrons originate due to a bombardment of the plasma electrode surface by ions of a driven ring and the thermoelectrons produced by a rare earth ceramic electrode, which is appropriately installed in the source chamber. The experimental and calculation data on the negative hydrogen ion generation rate demonstrate that very low-energy thermoelectrons significantly enhance the negative-ion generation rate that occurs in the layer adjacent to the plasma electrode surface. It is found that heating of the tungsten filaments placed in the source chamber improves the discharge stability and extends the pressure operation range.

Bond-length distributions for ions bonded to oxygen: results for the non-metals and discussion of lone-pair stereoactivity and the polymerization of PO4

PubMed Central

Gagné, Olivier Charles

2018-01-01

Bond-length distributions are examined for three configurations of the H+ ion, 16 configurations of the group 14–16 non-metal ions and seven configurations of the group 17 ions bonded to oxygen, for 223 coordination polyhedra and 452 bond distances for the H+ ion, 5957 coordination polyhedra and 22 784 bond distances for the group 14–16 non-metal ions, and 248 coordination polyhedra and 1394 bond distances for the group 17 non-metal ions. H⋯O and O—H + H⋯O distances correlate with O⋯O distance (R 2 = 0.94 and 0.96): H⋯O = 1.273 × O⋯O – 1.717 Å; O—H + H⋯O = 1.068 × O⋯O – 0.170 Å. These equations may be used to locate the hydrogen atom more accurately in a structure refined by X-ray diffraction. For non-metal elements that occur with lone-pair electrons, the most observed state between the n versus n+2 oxidation state is that of highest oxidation state for period 3 cations, and lowest oxidation state for period 4 and 5 cations when bonded to O2−. Observed O—X—O bond angles indicate that the period 3 non-metal ions P3+, S4+, Cl3+ and Cl5+ are lone-pair seteroactive when bonded to O2−, even though they do not form secondary bonds. There is no strong correlation between the degree of lone-pair stereoactivity and coordination number when including secondary bonds. There is no correlation between lone-pair stereoactivity and bond-valence sum at the central cation. In synthetic compounds, PO4 polymerizes via one or two bridging oxygen atoms, but not by three. Partitioning our PO4 dataset shows that multi-modality in the distribution of bond lengths is caused by the different bond-valence constraints that arise for Obr = 0, 1 and 2. For strongly bonded cations, i.e. oxyanions, the most probable cause of mean bond length variation is the effect of structure type, i.e. stress induced by the inability of a structure to follow its a priori bond lengths. For ions with stereoactive lone-pair electrons, the most probable cause of variation is bond-length distortion.

Na+-driven bacterial flagellar motors.

PubMed

Imae, Y; Atsumi, T

1989-12-01

Bacterial flagellar motors are the reversible rotary engine which propels the cell by rotating a helical flagellar filament as a screw propeller. The motors are embedded in the cytoplasmic membrane, and the energy for rotation is supplied by the electrochemical potential of specific ions across the membrane. Thus, the analysis of motor rotation at the molecular level is linked to an understanding of how the living system converts chemical energy into mechanical work. Based on the coupling ions, the motors are divided into two types; one is the H+-driven type found in neutrophiles such as Bacillus subtilis and Escherichia coli and the other is the Na+-driven type found in alkalophilic Bacillus and marine Vibrio. In this review, we summarize the current status of research on the rotation mechanism of the Na+-driven flagellar motors, which introduces several new aspects in the analysis.

Understanding the conductive channel evolution in Na:WO3-x-based planar devices

NASA Astrophysics Data System (ADS)

Shang, Dashan; Li, Peining; Wang, Tao; Carria, Egidio; Sun, Jirong; Shen, Baogen; Taubner, Thomas; Valov, Ilia; Waser, Rainer; Wuttig, Matthias

2015-03-01

An ion migration process in a solid electrolyte is important for ion-based functional devices, such as fuel cells, batteries, electrochromics, gas sensors, and resistive switching systems. In this study, a planar sandwich structure is prepared by depositing tungsten oxide (WO3-x) films on a soda-lime glass substrate, from which Na+ diffuses into the WO3-x films during the deposition. The entire process of Na+ migration driven by an alternating electric field is visualized in the Na-doped WO3-x films in the form of conductive channel by in situ optical imaging combined with infrared spectroscopy and near-field imaging techniques. A reversible change of geometry between a parabolic and a bar channel is observed with the resistance change of the devices. The peculiar channel evolution is interpreted by a thermal-stress-induced mechanical deformation of the films and an asymmetric Na+ mobility between the parabolic and the bar channels. These results exemplify a typical ion migration process driven by an alternating electric field in a solid electrolyte with a low ion mobility and are expected to be beneficial to improve the controllability of the ion migration in ion-based functional devices, such as resistive switching devices.An ion migration process in a solid electrolyte is important for ion-based functional devices, such as fuel cells, batteries, electrochromics, gas sensors, and resistive switching systems. In this study, a planar sandwich structure is prepared by depositing tungsten oxide (WO3-x) films on a soda-lime glass substrate, from which Na+ diffuses into the WO3-x films during the deposition. The entire process of Na+ migration driven by an alternating electric field is visualized in the Na-doped WO3-x films in the form of conductive channel by in situ optical imaging combined with infrared spectroscopy and near-field imaging techniques. A reversible change of geometry between a parabolic and a bar channel is observed with the resistance change of the devices. The peculiar channel evolution is interpreted by a thermal-stress-induced mechanical deformation of the films and an asymmetric Na+ mobility between the parabolic and the bar channels. These results exemplify a typical ion migration process driven by an alternating electric field in a solid electrolyte with a low ion mobility and are expected to be beneficial to improve the controllability of the ion migration in ion-based functional devices, such as resistive switching devices. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr07545e

An absorption spectral study of Nd (III) with glutathione (reduced), GSH in aqueous and aquated organic solvent in presence and absence of Zn (II)

NASA Astrophysics Data System (ADS)

Mehta, Jignasu P.; Bhatt, Prashant N.; Misra, Sudhindra N.

2003-02-01

The coordination chemistry of glutathione (reduced) GSH is of great importance as it acts as an excellent model system for the binding of metal ions. The GSH complexation with metal ions is involved in the toxicology of different metal ions. Its coordination behaviour for soft metal ions and hard metal ions is found different because of the structure of GSH and its different potential binding sites. We have studied two chemically dissimilar metal ions viz. Nd (III) being hard metal ion, which will prefer hard donor sites like carboxylic groups, and Zn (II) the soft metal ion more suited to peptide-NH and sulfhydryl groups. The absorption difference and comparative absorption spectroscopy involving 4f-4f transitions of the heterobimetallic complexation of GSH with Nd (III) and Zn (II) has been explored in aqueous and aquated organic solvents. The changes in the oscillator strengths of different 4f-4f bands and Judd-Ofelt intensity (Tλ) parameters determined experimentally is being used to investigate the complexation of GSH. The in vivo intracellular complexation of GSH with Ca (II) in presence of Zn (II) ion has been mimicked through Nd (III)-GSH-Zn (II) absorption spectral studies in vitro.

Acid-switched Eu(III) coordination inside reverse aggregates: Insights into a synergistic liquid-liquid extraction system

DOE PAGES

Ellis, Ross J.

2016-08-09

Determining the structure of complex solutions bearing metal ions is challenging, but crucial for developing important technologies such as liquid-liquid extraction for metal refining and separation purposes. Herein, the structure of an organic Eu(III) solution consisting a binary mixture of lipophilic ligands di-2-ethylhexyl phosphoric acid (HDEHP) and tetraoctyl diglycolamide (TODGA) in dodecane is studied using synchrotron small angle X-ray scattering (SAXS) and X-ray absorption fine structure spectroscopy (EXAFS). This system is of technological importance in f-element separation for nuclear fuel cycle applications, where extraction is controlled by varying nitric acid concentration. Extraction is promoted at low and high concentration, butmore » is retarded at intermediate concentration, leading to a U-shaped function; the structural origins of which we investigate. At the nanoscale, the solution is apparently comprised of reverse micelles with polar cores of approximately 1 nm in size, and these remain virtually unchanged as acid concentration is varied. Inside the polar cores, the coordination environment of Eu(III) switches from a 9-coordinate [Eu(TODGA) 3] 3+ motif at high acid, to a 6-coordinate HDEHP-dominated complex resembling Eu(HDEHP·DEHP) 3 at low acid. The results show that extraction is controlled within the coordination sphere, where it is promoted under conditions that favor coordination of either one of the two organic ligands, but is retarded under conditions that encourage mixed complexes. Lastly, our results link solution structure with ion transport properties in a technologically-important liquid-liquid ion extraction system.« less

Docking modes of BB-3497 into the PDF active site--a comparison of the pure MM and QM/MM based docking strategies.

PubMed

Kumari, Tripti; Issar, Upasana; Kakkar, Rita

2014-01-01

Peptide deformylase (PDF) has emerged as an important antibacterial drug target. Considerable effort is being directed toward developing peptidic and non-peptidic inhibitors for this metalloprotein. In this work, the known peptidic inhibitor BB-3497 and its various ionization and tautomeric states are evaluated for their inhibition efficiency against PDF using a molecular mechanics (MM) approach as well as a mixed quantum mechanics/molecular mechanics (QM/MM) approach, with an aim to understand the interactions in the binding site. The evaluated Gibbs energies of binding with the mixed QM/MM approach are shown to have the best predictive power. The experimental pose is found to have the most negative Gibbs energy of binding, and also the smallest strain energy. A quantum mechanical evaluation of the active site reveals the requirement of strong chelation by the ligand with the metal ion. The investigated ligand chelates the metal ion through the two oxygens of its reverse hydroxamate moiety, particularly the N-O(-) oxygen, forming strong covalent bonds with the metal ion, which is penta-coordinated. In the uninhibited state, the metal ion is tetrahedrally coordinated, and hence chelation with the inhibitor is associated with an increase of the metal ion coordination. Thus, the strong binding of the ligand at the binding site is accounted for.

Complexation-induced supramolecular assembly drives metal-ion extraction.

PubMed

Ellis, Ross J; Meridiano, Yannick; Muller, Julie; Berthon, Laurence; Guilbaud, Philippe; Zorz, Nicole; Antonio, Mark R; Demars, Thomas; Zemb, Thomas

2014-09-26

Combining experiment with theory reveals the role of self-assembly and complexation in metal-ion transfer through the water-oil interface. The coordinating metal salt Eu(NO3)3 was extracted from water into oil by a lipophilic neutral amphiphile. Molecular dynamics simulations were coupled to experimental spectroscopic and X-ray scattering techniques to investigate how local coordination interactions between the metal ion and ligands in the organic phase combine with long-range interactions to produce spontaneous changes in the solvent microstructure. Extraction of the Eu(3+)-3(NO3(-)) ion pairs involves incorporation of the "hard" metal complex into the core of "soft" aggregates. This seeds the formation of reverse micelles that draw the water and "free" amphiphile into nanoscale hydrophilic domains. The reverse micelles interact through attractive van der Waals interactions and coalesce into rod-shaped polynuclear Eu(III) -containing aggregates with metal centers bridged by nitrate. These preorganized hydrophilic domains, containing high densities of O-donor ligands and anions, provide improved Eu(III) solvation environments that help drive interfacial transfer, as is reflected by the increasing Eu(III) partitioning ratios (oil/aqueous) despite the organic phase approaching saturation. For the first time, this multiscale approach links metal-ion coordination with nanoscale structure to reveal the free-energy balance that drives the phase transfer of neutral metal salts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural and physical properties of transparent conducting, amorphous Zn-doped SnO2 films

NASA Astrophysics Data System (ADS)

Zhu, Q.; Ma, Q.; Buchholz, D. B.; Chang, R. P. H.; Bedzyk, M. J.; Mason, T. O.

2014-01-01

The structural and physical properties of conducting amorphous Zn-doped SnO2 (a-ZTO) films, prepared by pulsed laser deposition, were investigated as functions of oxygen deposition pressure (pO2), composition, and thermal annealing. X-ray scattering and X-ray absorption spectroscopy measurements reveal that at higher pO2, the a-ZTO films are highly transparent and have a structural framework similar to that found in crystalline (c-), rutile SnO2 in which the Sn4+ ion is octahedrally coordinated by 6 O2- ions. The Sn4+ ion in these films however has a coordination number (CN) smaller by 2%-3% than that in c-SnO2, indicating the presence of oxygen vacancies, which are the likely source of charge carriers. At lower pO2, the a-ZTO films show a brownish tint and contain some 4-fold coordinated Sn2+ ions. Under no circumstances is the CN around the Zn2+ ion larger than 4, and the Zn-O bond is shorter than the Sn-O bond by 0.07 Å. The addition of Zn has no impact on the electroneutrality but improves significantly the thermal stability of the films. Structural changes due to pO2, composition, and thermal annealing account well for the changes in the physical properties of a-ZTO films.

Hypoxia-driven angiogenesis: role of tip cells and extracellular matrix scaffolding.

PubMed

Germain, Stéphane; Monnot, Catherine; Muller, Laurent; Eichmann, Anne

2010-05-01

Angiogenesis is a highly coordinated tissue remodeling process leading to blood vessel formation. Hypoxia triggers angiogenesis via induction of expression of growth factors such as vascular endothelial growth factor (VEGF). VEGF instructs endothelial cells to form tip cells, which lead outgrowing capillary sprouts, whereas Notch signaling inhibits sprout formation. Basement membrane deposition and mechanical cues from the extracellular matrix (ECM) induced by hypoxia may participate to coordinated vessel sprouting in conjunction with the VEGF and Notch signaling pathways. Hypoxia regulates ECM composition, deposition, posttranslational modifications and rearrangement. In particular, hypoxia-driven vascular remodeling is dynamically regulated through modulation of ECM-modifying enzyme activities that eventually affect both matricellular proteins and growth factor availability. Better understanding of the complex interplay between endothelial cells and soluble growth factors and mechanical factors from the ECM will certainly have significant implications for understanding the regulation of developmental and pathological angiogenesis driven by hypoxia.

Direct Heating of a Laser-Imploded Core by Ultraintense Laser-Driven Ions

NASA Astrophysics Data System (ADS)

Kitagawa, Y.; Mori, Y.; Komeda, O.; Ishii, K.; Hanayama, R.; Fujita, K.; Okihara, S.; Sekine, T.; Satoh, N.; Kurita, T.; Takagi, M.; Watari, T.; Kawashima, T.; Kan, H.; Nishimura, Y.; Sunahara, A.; Sentoku, Y.; Nakamura, N.; Kondo, T.; Fujine, M.; Azuma, H.; Motohiro, T.; Hioki, T.; Kakeno, M.; Miura, E.; Arikawa, Y.; Nagai, T.; Abe, Y.; Ozaki, S.; Noda, A.

2015-05-01

A novel direct core heating fusion process is introduced, in which a preimploded core is predominantly heated by energetic ions driven by LFEX, an extremely energetic ultrashort pulse laser. Consequently, we have observed the D (d ,n )He 3 -reacted neutrons (DD beam-fusion neutrons) with the yield of 5 ×108 n /4 π sr . Examination of the beam-fusion neutrons verified that the ions directly collide with the core plasma. While the hot electrons heat the whole core volume, the energetic ions deposit their energies locally in the core, forming hot spots for fuel ignition. As evidenced in the spectrum, the process simultaneously excited thermal neutrons with the yield of 6 ×107 n /4 π sr , raising the local core temperature from 0.8 to 1.8 keV. A one-dimensional hydrocode STAR 1D explains the shell implosion dynamics including the beam fusion and thermal fusion initiated by fast deuterons and carbon ions. A two-dimensional collisional particle-in-cell code predicts the core heating due to resistive processes driven by hot electrons, and also the generation of fast ions, which could be an additional heating source when they reach the core. Since the core density is limited to 2 g /cm3 in the current experiment, neither hot electrons nor fast ions can efficiently deposit their energy and the neutron yield remains low. In future work, we will achieve the higher core density (>10 g /cm3 ); then hot electrons could contribute more to the core heating via drag heating. Together with hot electrons, the ion contribution to fast ignition is indispensable for realizing high-gain fusion. By virtue of its core heating and ignition, the proposed scheme can potentially achieve high gain fusion.

Fast ion stabilization of the ion temperature gradient driven modes in the Joint European Torus hybrid-scenario plasmas: a trigger mechanism for internal transport barrier formation

NASA Astrophysics Data System (ADS)

Romanelli, M.; Zocco, A.; Crisanti, F.; Contributors, JET-EFDA

2010-04-01

Understanding and modelling turbulent transport in thermonuclear fusion plasmas are crucial for designing and optimizing the operational scenarios of future fusion reactors. In this context, plasmas exhibiting state transitions, such as the formation of an internal transport barrier (ITB), are particularly interesting since they can shed light on transport physics and offer the opportunity to test different turbulence suppression models. In this paper, we focus on the modelling of ITB formation in the Joint European Torus (JET) [1] hybrid-scenario plasmas, where, due to the monotonic safety factor profile, magnetic shear stabilization cannot be invoked to explain the transition. The turbulence suppression mechanism investigated here relies on the increase in the plasma pressure gradient in the presence of a minority of energetic ions. Microstability analysis of the ion temperature gradient driven modes (ITG) in the presence of a fast-hydrogen minority shows that energetic ions accelerated by the ion cyclotron resonance heating (ICRH) system (hydrogen, nH,fast/nD,thermal up to 10%, TH,fast/TD,thermal up to 30) can increase the pressure gradient enough to stabilize the ITG modes driven by the gradient of the thermal ions (deuterium). Numerical analysis shows that, by increasing the temperature of the energetic ions, electrostatic ITG modes are gradually replaced by nearly electrostatic modes with tearing parity at progressively longer wavelengths. The growth rate of the microtearing modes is found to be lower than that of the ITG modes and comparable to the local E × B-velocity shearing rate. The above mechanism is proposed as a possible trigger for the formation of ITBs in this type of discharges.

Direct heating of a laser-imploded core by ultraintense laser-driven ions.

PubMed

Kitagawa, Y; Mori, Y; Komeda, O; Ishii, K; Hanayama, R; Fujita, K; Okihara, S; Sekine, T; Satoh, N; Kurita, T; Takagi, M; Watari, T; Kawashima, T; Kan, H; Nishimura, Y; Sunahara, A; Sentoku, Y; Nakamura, N; Kondo, T; Fujine, M; Azuma, H; Motohiro, T; Hioki, T; Kakeno, M; Miura, E; Arikawa, Y; Nagai, T; Abe, Y; Ozaki, S; Noda, A

2015-05-15

A novel direct core heating fusion process is introduced, in which a preimploded core is predominantly heated by energetic ions driven by LFEX, an extremely energetic ultrashort pulse laser. Consequently, we have observed the D(d,n)^{3}He-reacted neutrons (DD beam-fusion neutrons) with the yield of 5×10^{8} n/4π sr. Examination of the beam-fusion neutrons verified that the ions directly collide with the core plasma. While the hot electrons heat the whole core volume, the energetic ions deposit their energies locally in the core, forming hot spots for fuel ignition. As evidenced in the spectrum, the process simultaneously excited thermal neutrons with the yield of 6×10^{7} n/4π sr, raising the local core temperature from 0.8 to 1.8 keV. A one-dimensional hydrocode STAR 1D explains the shell implosion dynamics including the beam fusion and thermal fusion initiated by fast deuterons and carbon ions. A two-dimensional collisional particle-in-cell code predicts the core heating due to resistive processes driven by hot electrons, and also the generation of fast ions, which could be an additional heating source when they reach the core. Since the core density is limited to 2 g/cm^{3} in the current experiment, neither hot electrons nor fast ions can efficiently deposit their energy and the neutron yield remains low. In future work, we will achieve the higher core density (>10 g/cm^{3}); then hot electrons could contribute more to the core heating via drag heating. Together with hot electrons, the ion contribution to fast ignition is indispensable for realizing high-gain fusion. By virtue of its core heating and ignition, the proposed scheme can potentially achieve high gain fusion.

Comparison between Free and Immobilized Ion Effects on Hydrophobic Interactions: A Molecular Dynamics Study.

PubMed

Huang, Kai; Gast, Sebastian; Ma, C Derek; Abbott, Nicholas L; Szlufarska, Izabela

2015-10-15

Fundamental studies of the effect of specific ions on hydrophobic interactions are driven by the need to understand phenomena such as hydrophobically driven self-assembly or protein folding. Using β-peptide-inspired nanorods, we investigate the effects of both free ions (dissolved salts) and proximally immobilized ions on hydrophobic interactions. We find that the free ion effect is correlated with the water density fluctuation near a nonpolar molecular surface, showing that such fluctuation can be an indicator of hydrophobic interactions in the case of solution additives. In the case of immobilized ion, our results demonstrate that hydrophobic interactions can be switched on and off by choosing different spatial arrangements of proximal ions on a nanorod. For globally amphiphilic nanorods, we find that the magnitude of the interaction can be further tuned using proximal ions with varying ionic sizes. In general, univalent proximal anions are found to weaken hydrophobic interactions. This is in contrast to the effect of free ions, which according to our simulations strengthen hydrophobic interactions. In addition, immobilized anions of increasing ionic size do not follow the same ordering (Hofmeister-like ranking) as free ions when it comes to their impact on hydrophobic interactions. The immobilized ion effect is not simply correlated with the water density fluctuation near the nonpolar side of the amphiphilic nanorod. We propose a molecular picture that explains the contrasting effects of immobilized versus free ions.

Loose coupling in the bacterial flagellar motor

PubMed Central

Boschert, Ryan; Adler, Frederick R.; Blair, David F.

2015-01-01

Physiological properties of the flagellar rotary motor have been taken to indicate a tightly coupled mechanism in which each revolution is driven by a fixed number of energizing ions. Measurements that would directly test the tight-coupling hypothesis have not been made. Energizing ions flow through membrane-bound complexes formed from the proteins MotA and MotB, which are anchored to the cell wall and constitute the stator. Genetic and biochemical evidence points to a “power stroke” mechanism in which the ions interact with an aspartate residue of MotB to drive conformational changes in MotA that are transmitted to the rotor protein FliG. Each stator complex contains two separate ion-binding sites, raising the question of whether the power stroke is driven by one, two, or either number of ions. Here, we describe simulations of a model in which the conformational change can be driven by either one or two ions. This loosely coupled model can account for the observed physiological properties of the motor, including those that have been taken to indicate tight coupling; it also accords with recent measurements of motor torque at high load that are harder to explain in tight-coupling models. Under loads relevant to a swimming cell, the loosely coupled motor would perform about as well as a two-proton motor and significantly better than a one-proton motor. The loosely coupled motor is predicted to be especially advantageous under conditions of diminished energy supply, or of reduced temperature, turning faster than an obligatorily two-proton motor while using fewer ions. PMID:25825730

Lazy checkpoint coordination for bounding rollback propagation

NASA Technical Reports Server (NTRS)

Wang, Yi-Min; Fuchs, W. Kent

1992-01-01

Independent checkpointing allows maximum process autonomy but suffers from potential domino effects. Coordinated checkpointing eliminates the domino effect by sacrificing a certain degree of process autonomy. In this paper, we propose the technique of lazy checkpoint coordination which preserves process autonomy while employing communication-induced checkpoint coordination for bounding rollback propagation. The introduction of the notion of laziness allows a flexible trade-off between the cost for checkpoint coordination and the average rollback distance. Worst-case overhead analysis provides a means for estimating the extra checkpoint overhead. Communication trace-driven simulation for several parallel programs is used to evaluate the benefits of the proposed scheme for real applications.

Stabilization of sawteeth with third harmonic deuterium ICRF-accelerated beam in JET plasmas

NASA Astrophysics Data System (ADS)

Girardo, Jean-Baptiste; Sharapov, Sergei; Boom, Jurrian; Dumont, Rémi; Eriksson, Jacob; Fitzgerald, Michael; Garbet, Xavier; Hawkes, Nick; Kiptily, Vasily; Lupelli, Ivan; Mantsinen, Mervi; Sarazin, Yanick; Schneider, Mireille

2016-01-01

Sawtooth stabilisation by fast ions is investigated in deuterium (D) and D-helium 3 (He3) plasmas of JET heated by deuterium Neutral Beam Injection combined in synergy with Ion Cyclotron Resonance Heating (ICRH) applied on-axis at 3rd beam cyclotron harmonic. A very significant increase in the sawtooth period is observed, caused by the ICRH-acceleration of the beam ions born at 100 keV to the MeV energy range. Four representative sawteeth from four different discharges are compared with Porcelli's model. In two discharges, the sawtooth crash appears to be triggered by core-localized Toroidal Alfvén Eigenmodes inside the q = 1 surface (also called "tornado" modes) which expel the fast ions from within the q = 1 surface, over time scales comparable with the sawtooth period. Two other discharges did not exhibit fast ion-driven instabilities in the plasma core, and no degradation of fast ion confinement was found in both modelling and direct measurements of fast ion profile with the neutron camera. The developed sawtooth scenario without fast ion-driven instabilities in the plasma core is of high interest for the burning plasmas. Possible causes of the sawtooth crashes on JET are discussed.

Applications of Ultra-Intense, Short Laser Pulses

NASA Astrophysics Data System (ADS)

Ledingham, Ken W. D.

The high intensity laser production of electron, proton, ion and photon beams is reviewed particularly with respect to the laser-plasma interaction which drives the acceleration process. A number of applications for these intense short pulse beams is discussed e.g. ion therapy, PET isotope production and laser driven transmutation studies. The future for laser driven nuclear physics at the huge new, multi-petawatt proposed laser installation ELI in Bucharest is described. Many people believe this will take European nuclear research to the next level.

Comparison of energy interaction parameters for the complexation of Pr(III) with glutathione reduced (GSH) in absence and presence of Zn(II) in aqueous and aquated organic solvents using 4f?4f transition spectra as PROBE

NASA Astrophysics Data System (ADS)

Singh, Th. David; Sumitra, Ch.; Yaiphaba, N.; Devi, H. Debecca; Devi, M. Indira; Singh, N. Rajmuhon

2005-04-01

The coordination chemistry of glutathione reduced (GSH) is of great importance as it acts as excellent model system for the binding of metal ions. The GSH complexation with metal ions is involved in the toxicology of different metal ions. Its coordination behaviour for soft metal ions and hard metal ions is found different because of the structure of GSH and its different potential binding sites. In our work we have studied two chemically dissimilar metal ions viz. Pr(III), which prefer hard donor site like carboxylic groups and Zn(II) the soft metal ion which prefer peptide-NH and sulphydryl groups. The absorption difference and comparative absorption spectroscopy involving 4f-4f transitions of the heterobimetallic Complexation of GSH with Pr(III) and Zn(II) has been explored in aqueous and aquated organic solvents. The variation in the energy parameters like Slater-Condon ( F K), Racah ( E K) and Lande ( ξ4f), Nephelauxetic parameter ( β) and bonding parameter ( b1/2) are computed to explain the nature of complexation.

Insights on Li-TFSI diffusion in polyethylene oxide for battery applications

NASA Astrophysics Data System (ADS)

Molinari, Nicola; Mailoa, Jonathan; Kozinsky, Boris; Robert Bosch LLC Collaboration

Improving the energy density, safety and efficiency of lithium-ion (Li-ion) batteries is crucial for the future of energy storage and applications such as electric cars. A key step in the research of next-generation solid polymeric electrolyte materials is understanding the diffusion mechanism of Li-ion in polyethylene oxide (PEO) in order to guide the design of electrolytes materials with high Li-ion diffusion while, ideally, suppress counter-anion movement. In this work we use computer simulations to investigate this long-standing problem at a fundamental level. The system under study has Li-TFSI concentration and PEO chain length that are representative of practical application specifications; the interactions of the molecular model are described via the PCFF+ all-atom force-field. Validation of the model is performed by comparing trends against experiments for diffusivity and conductivity as a function of salt concentration. The analysis of Li-TFSI molecular dynamics trajectories reveals that 1. for high Li-TFSI concentration a significant fraction of Li-ion is coordinated by only TFSI and consistently move less than PEO-coordinated Li-ion, 2. PEO chain motion is key in enabling Li-ion movement. Robert Bosch LLC.

Strengthening of the Coordination Shell by Counter Ions in Aqueous Th 4+ Solutions

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

Atta-Fynn, Raymond; Bylaska, Eric J.; de Jong, Wibe A.

The presence of counter ions in solutions containing highly charged metal cations can trigger processes such as ion-pair formation, hydrogen bond breakages and subsequent reformation, and ligand exchanges. In this work, it is shown how halide (Cl-, Br-) and perchlorate (ClO4-) anions affect the strength of the primary solvent coordination shells around Th4+ using explicit solvent and finite temperature ab initio molecular dynamics modeling methods. The 9-fold solvent geometry was found to be the most stable hydration structure in each aqueous solution. Relative to the dilute aqueous solution, the presence of the counter ions did not significantly alter the geometrymore » of the primary hydration shell. However, the free energy analyses indicated that the 10-fold hydrated states were thermodynamically accessible in dilute and bromide aqueous solutions within 1 kcal/mol. Analysis of the results showed that the hydrogen bond lifetimes were longer and solvent exchange energy barriers were larger in solutions with counter ions in comparison with the solution with no counter ions. This implies that the presence of the counter ions induces a strengthening of the Th4+ hydration shell.« less

Cd(II) and Pb(II) complexes of the polyether ionophorous antibiotic salinomycin

PubMed Central

2011-01-01

Background The natural polyether ionophorous antibiotics are used for the treatment of coccidiosis in poultry and ruminants. They are effective agents against infections caused by Gram-positive microorganisms. On the other hand, it was found that some of these compounds selectively bind lead(II) ions in in vivo experiments, despite so far no Pb(II)-containing compounds of defined composition have been isolated and characterized. To assess the potential of polyether ionophores as possible antidotes in the agriculture, a detailed study on their in vitro complexation with toxic metal ions is required. In the present paper we report for the first time the preparation and the structure elucidation of salinomycin complexes with ions of cadmium(II) and lead(II). Results New metal(II) complexes of the polyether ionophorous antibiotic salinomycin with Cd(II) and Pb(II) ions were prepared and structurally characterized by IR, FAB-MS and NMR techniques. The spectroscopic information and elemental analysis data reveal that sodium salinomycin (SalNa) undergoes a reaction with heavy metal(II) ions to form [Cd(Sal)2(H2O)2] (1) and [Pb(Sal)(NO3)] (2), respectively. Abstraction of sodium ions from the cavity of the antibiotic is occurring during the complexation reaction. Salinomycin coordinates with cadmium(II) ions as a bidentate monoanionic ligand through the deprotonated carboxylic moiety and one of the hydroxyl groups to yield 1. Two salinomycin anions occupy the equatorial plane of the Cd(II) center, while two water molecules take the axial positions of the inner coordination sphere of the metal(II) cation. Complex 2 consists of monoanionic salinomycin acting in polydentate coordination mode in a molar ratio of 1: 1 to the metal ion with one nitrate ion for charge compensation. Conclusion The formation of the salinomycin heavy metal(II) complexes indicates a possible antidote activity of the ligand in case of chronic/acute intoxications likely to occur in the stock farming. PMID:21906282

A quasi-linear analysis of the impurity effect on turbulent momentum transport and residual stress

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

Ko, S. H., E-mail: shko@nfri.re.kr; Jhang, Hogun; Singh, R.

2015-08-15

We study the impact of impurities on turbulence driven intrinsic rotation (via residual stress) in the context of the quasi-linear theory. A two-fluid formulation for main and impurity ions is employed to study ion temperature gradient modes in sheared slab geometry modified by the presence of impurities. An effective form of the parallel Reynolds stress is derived in the center of mass frame of a coupled main ion-impurity system. Analyses show that the contents and the radial profile of impurities have a strong influence on the residual stress. In particular, an impurity profile aligned with that of main ions ismore » shown to cause a considerable reduction of the residual stress, which may lead to the reduction of turbulence driven intrinsic rotation.« less

Effects of eletron heating on the current driven electrostatic ion cyclotron instability and plasma transport processes along auroral field lines

NASA Technical Reports Server (NTRS)

Ganguli, Supriya B.; Mitchell, Horace G.; Palmadesso, Peter J.

1988-01-01

Fluid simulations of the plasma along auroral field lines in the return current region have been performed. It is shown that the onset of electrostatic ion cyclotron (EIC) related anomalous resistivity and the consequent heating of electrons leads to a transverse ion temperature that is much higher than that produced by the current driven EIC instability (CDICI) alone. Two processes are presented for the enhancement of ion heating by anomalous resistivity. The anomalous resistivity associated with the turbulence is limited by electron heating, so that CDICI saturates at transverse temperature that is substantially higher than in the absence of resistivity. It is suggested that this process demonstrates a positive feedback loop in the interaction between CDICI, anomalous resistivity, and parallel large-scale dynamics in the topside ionosphere.

Solar-Pumping Upconversion of Interfacial Coordination Nanoparticles.

PubMed

Ishii, Ayumi; Hasegawa, Miki

2017-01-30

An interfacial coordination nanoparticle successfully exhibited an upconversion blue emission excited by very low-power light irradiation, such as sunlight. The interfacial complex was composed of Yb ions and indigo dye, which formed a nano-ordered thin shell layer on a Tm 2 O 3 nanoparticle. At the surface of the Tm 2 O 3 particle, the indigo dye can be excited by non-laser excitation at 640 nm, following the intramolecular energy transfer from the indigo dye to the Yb ions. Additionally, the excitation energy of the Yb ion was upconverted to the blue emission of the Tm ion at 475 nm. This upconversion blue emission was achieved by excitation with a CW Xe lamp at an excitation power of 0.14 mW/cm 2 , which is significantly lower than the solar irradiation power of 1.4 mW/cm 2 at 640 ± 5 nm.

Polynuclear Speciation of Trivalent Cations near the Surface of an Electrolyte Solution

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

Bera, Mrinal K.; Antonio, Mark R.

Despite long-standing efforts, there is no agreed upon structural model for electrolyte solutions at air-liquid interfaces. We report the simultaneous detection of the near-surface and bulk coordination environments of a trivalent metal cation (europium) in an aqueous solution by use of X-ray absorption spectroscopy. Within the first few nanometers of the liquid surface, the cations exhibit oxygen coordination typical of inner-sphere hydration of an aquated Eu3+ cation. Beyond that, outer-sphere ion-ion correlations are observed that are otherwise not present in the bulk electrolyte. The combination of near-surface and bulk sensitivities to probe metal ion speciation in electrolyte solutions is achievedmore » by detecting electron-yield and X-ray fluorescence signals from an inverted pendant drop. The results provide new knowledge about the near-surface chemistry of aqueous solutions of relevance to aerosols and ion transport processes in chemical separations and biological systems.« less

Why are ionic liquid ions mainly associated in water? A Car-Parrinello study of 1-ethyl-3-methyl-imidazolium chloride water mixture

NASA Astrophysics Data System (ADS)

Spickermann, C.; Thar, J.; Lehmann, S. B. C.; Zahn, S.; Hunger, J.; Buchner, R.; Hunt, P. A.; Welton, T.; Kirchner, B.

2008-09-01

In this study we present the results of a first principles molecular dynamics simulation of a single 1-ethyl-3-methyl-imidazolium chloride [C2C1im][Cl] ion pair dissolved in 60 water molecules. We observe a preference of the in plane chloride coordination with respect to the cation ring plane as compared to the energetic slightly more demanding on top coordination. Evaluation of the different radial distribution functions demonstrates that the structure of the hydration shell around the ion pair differs significantly from bulk water and that no true ion pair dissociation in terms of completely autonomous solvation shells takes place on the timescale of the simulation. In addition, dipole moment distributions of the solvent in distinct solvation shells around different functional parts of the [C2C1im][Cl] ion pair are calculated from maximally localized Wannier functions. The analysis of these distributions gives evidence for a depolarization of water molecules close to the hydrophobic parts of the cation as well as close to the anion. Examination of the angular distribution of different OH(H2O )-X angles in turn shows a linear coordination of chloride accompanied by a tangential orientation of water molecules around the hydrophobic groups, being a typical feature of hydrophobic hydration. Based on these orientational aspects, a structural model for the obvious preference of ion pair association is developed, which justifies the associating behavior of solvated [C2C1im][Cl] ions in terms of an energetically favorable interface between the solvation shells of the anion and the hydrophobic parts of the cation.

Why are ionic liquid ions mainly associated in water? A Car-Parrinello study of 1-ethyl-3-methyl-imidazolium chloride water mixture.

PubMed

Spickermann, C; Thar, J; Lehmann, S B C; Zahn, S; Hunger, J; Buchner, R; Hunt, P A; Welton, T; Kirchner, B

2008-09-14

In this study we present the results of a first principles molecular dynamics simulation of a single 1-ethyl-3-methyl-imidazolium chloride [C(2)C(1)im][Cl] ion pair dissolved in 60 water molecules. We observe a preference of the in plane chloride coordination with respect to the cation ring plane as compared to the energetic slightly more demanding on top coordination. Evaluation of the different radial distribution functions demonstrates that the structure of the hydration shell around the ion pair differs significantly from bulk water and that no true ion pair dissociation in terms of completely autonomous solvation shells takes place on the timescale of the simulation. In addition, dipole moment distributions of the solvent in distinct solvation shells around different functional parts of the [C(2)C(1)im][Cl] ion pair are calculated from maximally localized Wannier functions. The analysis of these distributions gives evidence for a depolarization of water molecules close to the hydrophobic parts of the cation as well as close to the anion. Examination of the angular distribution of different OH(H(2)O)-X angles in turn shows a linear coordination of chloride accompanied by a tangential orientation of water molecules around the hydrophobic groups, being a typical feature of hydrophobic hydration. Based on these orientational aspects, a structural model for the obvious preference of ion pair association is developed, which justifies the associating behavior of solvated [C(2)C(1)im][Cl] ions in terms of an energetically favorable interface between the solvation shells of the anion and the hydrophobic parts of the cation.

Bio-inspired metal ions regulate the structure evolution of self-assembled peptide-based nanoparticles

NASA Astrophysics Data System (ADS)

Xu, An-Ping; Yang, Pei-Pei; Yang, Chao; Gao, Yu-Juan; Zhao, Xiao-Xiao; Luo, Qiang; Li, Xiang-Dan; Li, Li-Zhong; Wang, Lei; Wang, Hao

2016-07-01

We report an assembly and transformation process of a supramolecular module, BP-KLVFF-RGD (BKR) in solution and on specific living cell surfaces for imaging and treatment. The BKR self-assembled into nanoparticles, which further transformed into nanofibers in situ induced by coordination with Ca2+ ions.We report an assembly and transformation process of a supramolecular module, BP-KLVFF-RGD (BKR) in solution and on specific living cell surfaces for imaging and treatment. The BKR self-assembled into nanoparticles, which further transformed into nanofibers in situ induced by coordination with Ca2+ ions. Electronic supplementary information (ESI) available: Experimental details; Fig. S1-S9. See DOI: 10.1039/c6nr03580a

Self-Assembly of Coordinative Supramolecular Polygons with Open Binding Sites

PubMed Central

Zheng, Yao-Rong; Wang, Ming; Kobayashi, Shiho; Stang, Peter J.

2011-01-01

The design and synthesis of coordinative supramolecular polygons with open binding sites is described. Coordination-driven self-assembly of 2,6-bis(pyridin-4-ylethynyl)pyridine with 60° and 120° organoplatinum acceptors results in quantitative formation of a supramolecular rhomboid and hexagon, respectively, both bearing open pyridyl binding sites. The structures were determined by multinuclear (31P and 1H) NMR spectroscopy and electrospray ionization (ESI) mass spectrometry, along with a computational study. PMID:21516167

Self-Assembly of Coordinative Supramolecular Polygons with Open Binding Sites.

PubMed

Zheng, Yao-Rong; Wang, Ming; Kobayashi, Shiho; Stang, Peter J

2011-04-27

The design and synthesis of coordinative supramolecular polygons with open binding sites is described. Coordination-driven self-assembly of 2,6-bis(pyridin-4-ylethynyl)pyridine with 60° and 120° organoplatinum acceptors results in quantitative formation of a supramolecular rhomboid and hexagon, respectively, both bearing open pyridyl binding sites. The structures were determined by multinuclear ((31)P and (1)H) NMR spectroscopy and electrospray ionization (ESI) mass spectrometry, along with a computational study.

Bromidotetra­kis­(2-ethyl-1H-imidazole-κN 3)copper(II) bromide

PubMed Central

Godlewska, Sylwia; Kelm, Harald; Krüger, Hans-Jörg; Dołęga, Anna

2012-01-01

The CuII ion in the title mol­ecular salt, [CuBr(C5H8N2)4]Br, is coordinated in a square-pyramidal geometry by four N atoms of imidazole ligands and one bromide anion in the apical position. In the crystal, the ions are linked by N—H⋯Br hydrogen bonds involving both the coordinating and the free bromide species as acceptors. A C—H⋯Br inter­action is also observed. Overall, a three-dimensional network results. PMID:23468738

A Hybrid Kinetic Model of Asymmetric Thin Current Sheets with Sheared Flows in a Collisionless Plasma

DTIC Science & Technology

2010-12-27

z are aligned with those of the usual Geocentric Sun - Earth (aSE) coordinates. In this frame, +x points from the Earth to the Sun , +y points out of...current sheet (box) in the solar wind. x, y, and z are aligned with the aSE coordinates, with +X pointing from the Earth toward the Sun , +y out of the...account the exact ion orbits and such properties as the anisotropic and nondiagonal pressure tensor and sheared ion flows. Figure 1a shows a schematic

Infrared spectroscopy of extreme coordination: the carbonyls of U(+) and UO(2)(+).

PubMed

Ricks, Allen M; Gagliardi, Laura; Duncan, Michael A

2010-11-17

Uranium and uranium dioxide carbonyl cations produced by laser vaporization are studied with mass-selected ion infrared spectroscopy in the C-O stretching region. Dissociation patterns, spectra, and quantum chemical calculations establish that the fully coordinated ions are U(CO)(8)(+) and UO(2)(CO)(5)(+), with D(4d) square antiprism and D(5h) pentagonal bipyramid structures. Back-bonding in U(CO)(8)(+) causes a red-shifted CO stretch, but back-donation is inefficient for UO(2)(CO)(5)(+), producing a blue-shifted CO stretch characteristic of nonclassical carbonyls.

Syntheses, structures and properties of four 3D microporous lanthanide coordination polymers based on 3,5-pyrazoledicarboxylate and oxalate ligands

NASA Astrophysics Data System (ADS)

Song, Juan; Wang, Ji-Jiang; Hu, Huai-Ming; Wu, Qing-Ran; Xie, Juan; Dong, Fa-Xin; Yang, Meng-Lin; Xue, Gang-Lin

2014-04-01

Four three-dimensional lanthanide coordination polymers with reversible structural interconversions, [Ln2(Hpdc)2(C2O4)(H2O)4]n·2nH2O [Ln=Sm (1), Eu (2), Tb (3) and Dy (4)], have been synthesized by hydrothermal reactions of lanthanide nitrates with 3,5-pyrazoledicarboxylic (H3pdc) and oxalic acids. It is noteworthy that there is an in situ reaction in 1, in which H3pdc was decomposed into (ox)2- with Cu(II)-Sm(III) synergistic effect under hydrothermal conditions. These compounds are isostructural and crystallized in the monoclinic P21/c space group. The Ln(III) ions are eight-coordinated with dodecahedron coordination geometry. These polyhedra are linked by oxalate groups to form 1D zigzag chain, which are further connected by 3,5-pyrazoledicarboxylate to extend similar 3D frameworks with channels along c-axis in 1-4. These coordination polymers display the characteristic emission bands of the Ln(III) ions in the solid state and possess good thermal stabilities.

Heralded ions via ionization coincidence

NASA Astrophysics Data System (ADS)

McCulloch, A. J.; Speirs, R. W.; Wissenberg, S. H.; Tielen, R. P. M.; Sparkes, B. M.; Scholten, R. E.

2018-04-01

We demonstrate a method for the deterministic production of single ions by exploiting the correlation between an electron and associated ion following ionization. Coincident detection and feedback in combination with Coulomb-driven particle selection allows for high-fidelity heralding of ions at a high repetition rate. Extension of the scheme beyond time-correlated feedback to position- and momentum-correlated feedback will provide a general and powerful means to optimize the ion beam brightness for the development of next-generation focused ion beam technologies.

Tuning the chromaticity of the emission color of the copolymers containing Eu(III), Tb(III), Be(II) ions based on colorimetric principle

NASA Astrophysics Data System (ADS)

Zhang, Aiqin; Yang, Yamin; Zhai, Guangmei; Jia, Husheng; Xu, Bingshe

2016-02-01

In this work, a method of tuning the chromaticity of the emission color of the copolymers containing Eu(III), Tb(III), Be(II) ions based on colorimetric principle was proposed. The technological route from coordination to copolymerization was employed to obtain the white light macromolecular phosphor. The three primary color monomers have been synthesized and their Commission Internationale de L'Eclairage (CIE) coordinates are respectively (0.540, 0.314), (0.231, 0.463), and (0.161, 0.054). The molar feed ratios of the three primary color monomers were calculated from the CIE coordinates based on colorimetric principle. Serial copolymers have been synthesized by free radical copolymerization of the three primary color monomers and methyl methacrylate. The quantum efficiency of the copolymers was higher than that of the complex monomers. The complexes were directly boned to the polymer chain, in which the energy transfer was reduced significantly compared to the doped-polymers. The experimental values of copolymers' CIE coordinates were located in the white light region in good agreement with theoretical values. The results indicate that the chromaticity of the emission color of the copolymers containing Eu(III), Tb(III), Be(II) ions could be tuned by theoretical calculation based on colorimetric principle.

Syntheses, crystal structures and characterizations of new zinc (II) and lead (II) carboxylate-phosphonates

NASA Astrophysics Data System (ADS)

Song, Jun-Ling; Mao, Jiang-Gao

2005-04-01

The syntheses, crystal structures and characterizations of two new divalent metal carboxylate-phosphonates, namely, Zn(H 3L)·2H 2O ( 1) and Pb(H 3L)(H 2O) 2 ( 2) (H 5L dbnd6 4-HO 2C-C 6H 4-CH 2N(CH 2PO 3H 2) 2) have been reported. Compound 1 features a 1D column structure in which the Zn(II) ions are tetrahedrally coordinated by four phosphonate oxygen atoms from four phosphonate ligands, and neighboring such 1D building blocks are further interconnected via hydrogen bonds into a 3D network. The carboxylate group of H 3L anion remains non-coordinated. Compound 2 has a 2D layer structure. Pb(II) ion is 7-coordinated by four phosphonate oxygen atoms from four phosphonate ligands and three aqua ligands. The interconnection of Pb(II) ions via bridging H 3L anions results in a <001> layer. The carboxylate group of the H 3L anion also remains non-coordinated and is oriented toward the interlayer space. Solid state luminescent spectrum of compound 1 exhibits a strong broad blue fluorescent emission band at 455 nm under excitation at 365 nm at room temperature.

Regulation of electron temperature gradient turbulence by zonal flows driven by trapped electron modes

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

Asahi, Y., E-mail: y.asahi@nr.titech.ac.jp; Tsutsui, H.; Tsuji-Iio, S.

2014-05-15

Turbulent transport caused by electron temperature gradient (ETG) modes was investigated by means of gyrokinetic simulations. It was found that the ETG turbulence can be regulated by meso-scale zonal flows driven by trapped electron modes (TEMs), which are excited with much smaller growth rates than those of ETG modes. The zonal flows of which radial wavelengths are in between the ion and the electron banana widths are not shielded by trapped ions nor electrons, and hence they are effectively driven by the TEMs. It was also shown that an E × B shearing rate of the TEM-driven zonal flows is larger thanmore » or comparable to the growth rates of long-wavelength ETG modes and TEMs, which make a main contribution to the turbulent transport before excitation of the zonal flows.« less

Crystal structures of two mononuclear complexes of terbium(III) nitrate with the tripodal alcohol 1,1,1-tris­(hy­droxy­meth­yl)propane

PubMed Central

Gregório, Thaiane; Giese, Siddhartha O. K.; Nunes, Giovana G.; Soares, Jaísa F.; Hughes, David L.

2017-01-01

Two new mononuclear cationic complexes in which the TbIII ion is bis-chelated by the tripodal alcohol 1,1,1-tris­(hy­droxy­meth­yl)propane (H3 L Et, C6H14O3) were prepared from Tb(NO3)3·5H2O and had their crystal and mol­ecular structures solved by single-crystal X-ray diffraction analysis after data collection at 100 K. Both products were isolated in reasonable yields from the same reaction mixture by using different crystallization conditions. The higher-symmetry complex dinitratobis[1,1,1-tris­(hy­droxy­meth­yl)propane]­terbium(III) nitrate di­meth­oxy­ethane hemisolvate, [Tb(NO3)2(H3 L Et)2]NO3·0.5C4H10O2, 1, in which the lanthanide ion is 10-coordinate and adopts an s-bicapped square-anti­prismatic coordination geometry, contains two bidentate nitrate ions bound to the metal atom; another nitrate ion functions as a counter-ion and a half-mol­ecule of di­meth­oxy­ethane (completed by a crystallographic twofold rotation axis) is also present. In product aqua­nitratobis[1,1,1-tris­(hy­droxy­meth­yl)propane]­terbium(III) dinitrate, [Tb(NO3)(H3 L Et)2(H2O)](NO3)2, 2, one bidentate nitrate ion and one water mol­ecule are bound to the nine-coordinate terbium(III) centre, while two free nitrate ions contribute to charge balance outside the tricapped trigonal-prismatic coordination polyhedron. No free water mol­ecule was found in either of the crystal structures and, only in the case of 1, di­meth­oxy­ethane acts as a crystallizing solvent. In both mol­ecular structures, the two tripodal ligands are bent to one side of the coordination sphere, leaving room for the anionic and water ligands. In complex 2, the methyl group of one of the H3 L Et ligands is disordered over two alternative orientations. Strong hydrogen bonds, both intra- and inter­molecular, are found in the crystal structures due to the number of different donor and acceptor groups present. PMID:28217359

Thermal Electron Contributions to Current-Driven Instabilities: SCIFER Observations in the 1400-km Cleft Ion Fountain and Their Implications to Thermal Ion Energization

NASA Technical Reports Server (NTRS)

Adrian, Mark L.; Pollock, C. J.; Moore, T. E.; Kintner, P. M.; Arnoldy, R. L.; Whitaker, Ann F. (Technical Monitor)

2001-01-01

SCIFER TECHS observations of the variations in the thermal electron distribution in the 1400-km altitude cleft are associated with periods of intense ion heating and field-aligned currents. Energization of the thermal ion plasma in the mid-altitude cleft occurs within density cavities accompanied by enhanced thermal electron temperatures, large field-aligned thermal electron plasma flows and broadband low-frequency electric fields. Variations in the thermal electron contribution to field-aligned current densities indicate small scale (approximately 100's m) filamentary structure embedded within the ion energization periods. TECHS observations of the field-aligned drift velocities and temperatures of the thermal electron distribution are presented to evaluate the critical velocity thresholds necessary for the generation of electrostatic ion cyclotron and ion acoustic instabilities. This analysis suggests that, during periods of thermal ion energization, sufficient drift exists in the thermal electron distribution to excite the electrostatic ion cyclotron instability. In addition, brief periods exist within the same interval where the drift of the thermal electron distribution is sufficient to marginally excite the ion acoustic instability. In addition, the presence an enhancement in Langmuir emission at the plasma frequency at the center of the ion energization region, accompanied by the emission's second-harmonic, and collocated with observations of high-frequency electric field solitary structures suggest the presence of electron beam driven decay of Langmuir waves to ion acoustic modes as an additional free energy source for ion energization.

Polymer matrix electroluminescent materials and devices

DOEpatents

Marrocco, III, Matthew L.; Motamedi, Farshad J [Claremont, CA; Abdelrazzaq, Feras Bashir [Covina, CA; Abdelrazzaq, legal representative, Bashir Twfiq

2012-06-26

Photoluminescent and electroluminescent compositions are provided which comprise a matrix comprising aromatic repeat units covalently coordinated to a phosphorescent or luminescent metal ion or metal ion complexes. Methods for producing such compositions, and the electroluminescent devices formed therefrom, are also disclosed.

Hydrated Cations in the General Chemistry Course.

ERIC Educational Resources Information Center

Kauffman, George B.; Baxter, John F., Jr.

1981-01-01

Presents selected information regarding the descriptive chemistry of the common metal ions and their compounds, including the concepts of process of solution, polar molecules, ionic size and charge, complex ions, coordination number, and the Bronsted-Lowry acid-base theory. (CS)

Uncoupling and Turnover in a Cl−/H+ Exchange Transporter

PubMed Central

Walden, Michael; Accardi, Alessio; Wu, Fang; Xu, Chen; Williams, Carole; Miller, Christopher

2007-01-01

The CLC-family protein CLC-ec1, a bacterial homologue of known structure, stoichiometrically exchanges two Cl− for one H+ via an unknown membrane transport mechanism. This study examines mutations at a conserved tyrosine residue, Y445, that directly coordinates a Cl− ion located near the center of the membrane. Mutations at this position lead to “uncoupling,” such that the H+/Cl− transport ratio decreases roughly with the volume of the substituted side chain. The uncoupled proteins are still able to pump protons uphill when driven by a Cl− gradient, but the extent and rate of this H+ pumping is weaker in the more uncoupled variants. Uncoupling is accompanied by conductive Cl− transport that is not linked to counter-movement of H+, i.e., a “leak.” The unitary Cl− transport rate, measured in reconstituted liposomes by both a conventional initial-velocity method and a novel Poisson dilution approach, is ∼4,000 s−1 for wild-type protein, and the uncoupled mutants transport Cl− at similar rates. PMID:17389248

Electrohydrodynamically driven large-area liquid ion sources

DOEpatents

Pregenzer, Arian L.

1988-01-01

A large-area liquid ion source comprises means for generating, over a large area of the surface of a liquid, an electric field of a strength sufficient to induce emission of ions from a large area of said liquid. Large areas in this context are those distinct from emitting areas in unidimensional emitters.

The LILIA (laser induced light ions acceleration) experiment at LNF

NASA Astrophysics Data System (ADS)

Agosteo, S.; Anania, M. P.; Caresana, M.; Cirrone, G. A. P.; De Martinis, C.; Delle Side, D.; Fazzi, A.; Gatti, G.; Giove, D.; Giulietti, D.; Gizzi, L. A.; Labate, L.; Londrillo, P.; Maggiore, M.; Nassisi, V.; Sinigardi, S.; Tramontana, A.; Schillaci, F.; Scuderi, V.; Turchetti, G.; Varoli, V.; Velardi, L.

2014-07-01

Laser-matter interaction at relativistic intensities opens up new research fields in the particle acceleration and related secondary sources, with immediate applications in medical diagnostics, biophysics, material science, inertial confinement fusion, up to laboratory astrophysics. In particular laser-driven ion acceleration is very promising for hadron therapy once the ion energy will attain a few hundred MeV. The limited value of the energy up to now obtained for the accelerated ions is the drawback of such innovative technique to the real applications. LILIA (laser induced light ions acceleration) is an experiment now running at LNF (Frascati) with the goal of producing a real proton beam able to be driven for significant distances (50-75 cm) away from the interaction point and which will act as a source for further accelerating structure. In this paper the description of the experimental setup, the preliminary results of solid target irradiation and start to end simulation for a post-accelerated beam up to 60 MeV are given.

Shear-flow driven dissipative instability and investigation of nonlinear drift-vortex modes in dusty plasmas with non-thermal ion population

NASA Astrophysics Data System (ADS)

Gul-e-Ali, Masood, W.; Mirza, Arshad M.

2017-12-01

The shear flow in dust dynamics driven waves in combination with the dust-neutral drag is studied in a plasma comprising of ions, electrons, and dust. Non-thermal population of ions is considered, which has been observed by many satellite missions. It is found that the dissipative instability produced by dust sheared flow and dust-neutral drag gets modified by the presence of nonthermal ions. It is found that the dissipative instability enhances for the Cairns distribution, whereas the kappa distribution arrests the growth of this instability. In the nonlinear regime, the formation of vortices in the system is studied. It is found that the nonthermal population of ions significantly alters these structures in comparison with their Maxwellian counterpart. The results obtained in this paper may have relevance in the planetary magnetospheres where the dust particles are present and non-Maxwellian distribution of particles have been observed by Freja and Viking satellites.

a Compact, Rf-Driven Pulsed Ion Source for Intense Neutron Generation

NASA Astrophysics Data System (ADS)

Perkins, L. T.; Celata, C. M.; Lee, Y.; Leung, K. N.; Picard, D. S.; Vilaithong, R.; Williams, M. D.; Wutte, D.

1997-05-01

Lawrence Berkeley National Laboratory is currently developing a compact, sealed-accelerator-tube neutron generator capable of producing a neutron flux in the range of 109 to 1010 D-T neutrons per second. The ion source, a miniaturized variation of earlier 2 MHz radio-frequency (rf)-driven multicusp ion sources, is designed to fit within a #197# 5 cm diameter borehole. Typical operating parameters include repetition rates up to 100 pps, with pulse widths between 10 and 80 us and source pressures as low as #197# 5 mTorr. In this configuration, peak extractable hydrogen current exceeding 35 mA from a 2 mm diameter aperture together with H1+ yields over 94% have been achieved. The required rf impedance matching network has been miniaturized to #197# 5 cm diameter. The accelerator column is a triode design using the IGUN ion optics codes and allows for electron suppression. Results from the testing of the integrated matching network-ion source-accelerator system will be presented.

Coordination of heterogeneous nonlinear multi-agent systems with prescribed behaviours

NASA Astrophysics Data System (ADS)

Tang, Yutao

2017-10-01

In this paper, we consider a coordination problem for a class of heterogeneous nonlinear multi-agent systems with a prescribed input-output behaviour which was represented by another input-driven system. In contrast to most existing multi-agent coordination results with an autonomous (virtual) leader, this formulation takes possible control inputs of the leader into consideration. First, the coordination was achieved by utilising a group of distributed observers based on conventional assumptions of model matching problem. Then, a fully distributed adaptive extension was proposed without using the input of this input-output behaviour. An example was given to verify their effectiveness.

Design Challenges of a Rapid Cycling Synchrotron for Carbon/Proton Therapy

NASA Astrophysics Data System (ADS)

Cook, Nathan

2012-03-01

The growing interest in radiation therapy with protons and light ions has driven demand for new methods of ion acceleration and the delivery of ion beams. One exciting new platform for ion beam acceleration and delivery is the rapid cycling synchrotron. Operating at 15Hz, rapid cycling achieves faster treatment times by making beam extraction possible at any energy during the cycle. Moreover, risk to the patient is reduced by requiring fewer particles in the beam line at a given time, thus eliminating the need for passive filtering and reducing the consequences of a malfunction. Lastly, the ability to switch between carbon ion and proton beam therapy provides the machine with an unmatched flexibility. However, these features do stipulate challenges in accelerator design. Maintaining a compact lattice requires careful tuning of lattice functions, tight focusing combined function magnets, and fast injection and extraction systems. Providing the necessary acceleration over a short cycle time also necessitates a five-fold frequency swing for carbon ions, further burdening the design requirements of ferrite-driven radiofrequency cavities. We will consider these challenges as well as some solutions selected for our current design.

Laser-driven atomic-probe-beam diagnostics

NASA Astrophysics Data System (ADS)

Knyazev, B. A.; Greenly, J. B.; Hammer, D. A.

2000-12-01

A new laser-driven atomic-probe-beam diagnostic (LAD) is proposed for local, time-resolved measurements of electric field and ion dynamics in the accelerating gap of intense ion beam diodes. LAD adds new features to previous Stark-shift diagnostics which have been progressively developed in several laboratories, from passive observation of Stark effect on ion species or fast (charge-exchanged) neutrals present naturally in diodes, to active Stark atomic spectroscopy (ASAS) in which selected probe atoms were injected into the gap and excited to suitable states by resonant laser radiation. The LAD scheme is a further enhancement of ASAS in which the probe atoms are also used as a local (laser-ionized) ion source at an instant of time. Analysis of the ion energy and angular distribution after leaving the gap enables measurement, at the chosen ionization location in the gap, of both electrostatic potential and the development of ion divergence. Calculations show that all of these quantities can be measured with sub-mm and ns resolution. Using lithium or sodium probe atoms, fields from 0.1 to 10 MV/cm can be measured.

The coordination of boundary tones and its interaction with prominence.

PubMed

Katsika, Argyro; Krivokapić, Jelena; Mooshammer, Christine; Tiede, Mark; Goldstein, Louis

2014-05-01

This study investigates the coordination of boundary tones as a function of stress and pitch accent. Boundary tone coordination has not been experimentally investigated previously, and the effect of prominence on this coordination, and whether it is lexical (stress-driven) or phrasal (pitch accent-driven) in nature is unclear. We assess these issues using a variety of syntactic constructions to elicit different boundary tones in an Electromagnetic Articulography (EMA) study of Greek. The results indicate that the onset of boundary tones co-occurs with the articulatory target of the final vowel. This timing is further modified by stress, but not by pitch accent: boundary tones are initiated earlier in words with non-final stress than in words with final stress regardless of accentual status. Visual data inspection reveals that phrase-final words are followed by acoustic pauses during which specific articulatory postures occur. Additional analyses show that these postures reach their achievement point at a stable temporal distance from boundary tone onsets regardless of stress position. Based on these results and parallel findings on boundary lengthening reported elsewhere, a novel approach to prosody is proposed within the context of Articulatory Phonology: rather than seeing prosodic (lexical and phrasal) events as independent entities, a set of coordination relations between them is suggested. The implications of this account for prosodic architecture are discussed.

N-(sulfoethyl) iminodiacetic acid-based lanthanide coordination polymers: Synthesis, magnetism and quantum Monte Carlo studies

NASA Astrophysics Data System (ADS)

Zhuang, Gui-lin; Chen, Wu-lin; Zheng, Jun; Yu, Hui-you; Wang, Jian-guo

2012-08-01

A series of lanthanide coordination polymers have been obtained through the hydrothermal reaction of N-(sulfoethyl) iminodiacetic acid (H3SIDA) and Ln(NO3)3 (Ln=La, 1; Pr, 2; Nd, 3; Gd, 4). Crystal structure analysis exhibits that lanthanide ions affect the coordination number, bond length and dimension of compounds 1-4, which reveal that their structure diversity can be attributed to the effect of lanthanide contraction. Furthermore, the combination of magnetic measure with quantum Monte Carlo(QMC) studies exhibits that the coupling parameters between two adjacent Gd3+ ions for anti-anti and syn-anti carboxylate bridges are -1.0×10-3 and -5.0×10-3 cm-1, respectively, which reveals weak antiferromagnetic interaction in 4.

Off-equatorial current-driven instabilities ahead of approaching dipolarization fronts

NASA Astrophysics Data System (ADS)

Zhang, Xu; Angelopoulos, V.; Pritchett, P. L.; Liu, Jiang

2017-05-01

Recent kinetic simulations have revealed that electromagnetic instabilities near the ion gyrofrequency and slightly away from the equatorial plane can be driven by a current parallel to the magnetic field prior to the arrival of dipolarization fronts. Such instabilities are important because of their potential contribution to global electromagnetic energy conversion near dipolarization fronts. Of the several instabilities that may be consistent with such waves, the most notable are the current-driven electromagnetic ion cyclotron instability and the current-driven kink-like instability. To confirm the existence and characteristics of these instabilities, we used observations by two Time History of Events and Macroscale Interactions during Substorms satellites, one near the neutral sheet observing dipolarization fronts and the other at the boundary layer observing precursor waves and currents. We found that such instabilities with monochromatic signatures are rare, but one of the few cases was selected for further study. Two different instabilities, one at about 0.3 Hz and the other at a much lower frequency, 0.02 Hz, were seen in the data from the off-equatorial spacecraft. A parallel current attributed to an electron beam coexisted with the waves. Our instability analysis attributes the higher-frequency instability to a current-driven ion cyclotron instability and the lower frequency instability to a kink-like instability. The current-driven kink-like instability we observed is consistent with the instabilities observed in the simulation. We suggest that the currents needed to excite these low-frequency instabilities are so intense that the associated electron beams are easily thermalized and hence difficult to observe.

Robustness of waves with a high phase velocity

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

Tajima, T., E-mail: ttajima@uci.edu; Tri Alpha Energy, Inc., P.O. Box 7010, Rancho Santa Margarita, CA 92688; Necas, A., E-mail: anecas@trialphaenergy.com

Norman Rostoker pioneered research of (1) plasma-driven accelerators and (2) beam-driven fusion reactors. The collective acceleration, coined by Veksler, advocates to drive above-ionization plasma waves by an electron beam to accelerate ions. The research on this, among others, by the Rostoker group incubated the idea that eventually led to the birth of the laser wakefield acceleration (LWFA), by which a large and robust accelerating collective fields may be generated in plasma in which plasma remains robust and undisrupted. Besides the emergence of LWFA, the Rostoker research spawned our lessons learned on the importance of adiabatic acceleration of ions in collectivemore » accelerators, including the recent rebirth in laser-driven ion acceleration efforts in a smooth adiabatic fashion by a variety of ingenious methods. Following Rostoker’s research in (2), the beam-driven Field Reversed Configuration (FRC) has accomplished breakthroughs in recent years. The beam-driven kinetic plasma instabilities have been found to drive the reactivity of deuteron-deuteron fusion beyond the thermonuclear yield in C-2U plasma that Rostoker started. This remarkable result in FRCs as well as the above mentioned LWFA may be understood with the aid of the newly introduced idea of the “robustness hypothesis of waves with a high phase velocity”. It posits that when the wave driven by a particle beam (or laser pulse) has a high phase velocity, its amplitude is high without disrupting the supporting bulk plasma. This hypothesis may guide us into more robust and efficient fusion reactors and more compact accelerators.« less

Heteroditopic receptors for ion-pair recognition.

PubMed

McConnell, Anna J; Beer, Paul D

2012-05-21

Ion-pair recognition is a new field of research emerging from cation and anion coordination chemistry. Specific types of heteroditopic receptor designs for ion pairs and the complexity of ion-pair binding are discussed to illustrate key concepts such as cooperativity. The importance of this area of research is reflected by the wide variety of potential applications of ion-pair receptors, including applications as membrane transport and salt solubilization agents and sensors. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metal-air cell with performance enhancing additive

DOEpatents

Friesen, Cody A; Buttry, Daniel

2015-11-10

Systems and methods drawn to an electrochemical cell comprising a low temperature ionic liquid comprising positive ions and negative ions and a performance enhancing additive added to the low temperature ionic liquid. The additive dissolves in the ionic liquid to form cations, which are coordinated with one or more negative ions forming ion complexes. The electrochemical cell also includes an air electrode configured to absorb and reduce oxygen. The ion complexes improve oxygen reduction thermodynamics and/or kinetics relative to the ionic liquid without the additive.

Determining the structure of tetragonal Y 2WO 6 and the site occupation of Eu 3+ dopant

NASA Astrophysics Data System (ADS)

Huang, Jinping; Xu, Jun; Li, Hexing; Luo, Hongshan; Yu, Xibin; Li, Yikang

2011-04-01

The compound Y 2WO 6 is prepared by solid state reaction at 750 °C using sodium chloride as mineralizer. Its structure is solved by ab-initio methods from X-ray powder diffraction data. This low temperature phase of yttrium tungstate crystallizes in tetragonal space group P4/ nmm (No. 129), Z=2, a=5.2596(2) Å, c=8.4158(4) Å. The tungsten atoms in the structure adopt an unusual [WO 6] distorted cubes coordination, connecting [YO 6] distorted cubes with oxygen vacancies at the O 2 layers while other yttrium ions Y 2 form [YO 8] cube coordination. Y 3+ ions occupy two crystallographic sites of 2 c ( C4v symmetry) and 2 a ( D2d symmetry) in the Y 2WO 6 host lattice. With Eu 3+ ions doped, the high resolution emission spectrum of Y 2WO 6:Eu 3+ suggests that Eu 3+ partly substituted for Y 3+ in these two sites. The result of the Rietveld structure refinement shows that the Eu 3+ dopants preferentially enter the 2 a site. The uniform cube coordination environment of Eu 3+ ions with the identical eight Eu-O bond lengths is proposed to be responsible for the intense excitation of long wavelength ultraviolet at 466-535 nm.

Molecular dynamics simulations of glycosyltransferase LgtC.

PubMed

Snajdrová, Lenka; Kulhánek, Petr; Imberty, Anne; Koca, Jaroslav

2004-04-02

Molecular dynamics simulations have been performed on fully solvated alpha-(1-->4)-galactosyltransferase LgtC from Neisseria meningitidis with and without the donor substrate UDP-Gal and in the presence of the manganese ion. The analysis of the trajectories revealed a limited movement in the loop X (residues 75-80) and a larger conformational change in the loop Y (residues 246-251) in the simulation, when UDP-Gal was not present. In this case, the loops X and Y open by almost 10A, exposing the active site to the solvent. The 'hinge region' responsible for the opening is composed of residues 246-247. We have also analyzed the behavior of the manganese ion in the simulations. The coordination number is 6 when UDP-Gal is present and it increases to 7 when it is absent. In the latter case, three water molecules become coordinated to the ion. In both cases, the coordination is very stable implying that the manganese ion is tightly bound in the active site of the enzyme even if UDP-Gal is not present. Further analysis of the structural water molecules location confirmed that the mobility of water molecules in the active site and the accessibility of this site for solvent are higher in the absence of the substrate.

Investigation of luminescence and laser transition of Dy3+ ion in P2O5sbnd PbOsbnd Bi2O3sbnd R2O3 (R = Al, Ga, In) glasses

NASA Astrophysics Data System (ADS)

Ram, G. Chinna; Narendrudu, T.; Suresh, S.; Kumar, A. Suneel; Rao, M. V. Sambasiva; Kumar, V. Ravi; Rao, D. Krishna

2017-04-01

P2O5sbnd PbOsbnd Bi2O3sbnd R2O3 (R = Al, Ga, In) glasses doped with Dy2O3 were prepared by melt quenching technique. The prepared glasses were characterized by XRD, optical absorption, FTIR, luminescence studies. Judd-Ofelt parameters have been evaluated for three glass systems from optical absorption spectra and in turn radiative parameters for excited luminescent levels of Dy3+ ion are also calculated. Emission cross section and branching ratio values are observed to high for 6H13/2 level for Dy3+ ion. The yellow to blue intensity ratios and CIE chromaticity coordinates were calculated. Decay curves exhibit non exponential behavior. Quantum efficiency of prepared glasses was measured by using radiative and calculated life times. IR studies, J-O parameters and Y/B ratio values indicate that more asymmetry around Dy3+ ions in Ga2O3 mixed glass was observed. Chromaticity coordinates lie near ideal white light region. These coordinates and CCT values have revealed that all the prepared glasses emit quality white light especially the glasses mixed with Ga2O3 are suitable for development of white LEDs.

Lead and selenite adsorption at water–goethite interfaces from first principles

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

Leung, Kevin; Criscenti, Louise J.

Here, the complexation of toxic and/or radioactive ions on to mineral surfaces is an important topic in geochemistry. We apply periodic-boundary-conditions density functional theory (DFT) molecular dynamics simulations to examine the coordination of Pb(II),more » $${\\rm SeO}_3^{2-}$$ , and their contact ion pairs to goethite (1 0 1) and (2 1 0) surfaces. The multitude of Pb(II) adsorption sites and possibility of Pb(II)-induced FeOH deprotonation make this a complex problem. At surface sites where Pb(II) is coordinated to three FeO and/or FeOH groups, and with judicious choices of FeOH surface group protonation states, the predicted Fe–Pb distances are in good agreement with EXAFS measurements. Trajectories where Pb(II) is in part coordinated to only two surface Fe–O groups exhibit larger fluctuations in Pb–O distances. Pb(II)/$${\\rm SeO}_3^{2-}$$ contact ion pairs are at least metastable on goethite (2 1 0) surfaces if the $${\\rm SeO}_3^{2-}$$ has a monodentate Se–O–Fe bond. Our DFT-based molecular dynamics calculations are a prerequisite for calculations of finite temperature equilibrium binding constants of Pb(II) and Pb(II)/$${\\rm SeO}_3^{2-}$$ ion pairs to goethite adsorption sites.« less

Lead and selenite adsorption at water–goethite interfaces from first principles

DOE PAGES

Leung, Kevin; Criscenti, Louise J.

2017-08-04

Here, the complexation of toxic and/or radioactive ions on to mineral surfaces is an important topic in geochemistry. We apply periodic-boundary-conditions density functional theory (DFT) molecular dynamics simulations to examine the coordination of Pb(II),more » $${\\rm SeO}_3^{2-}$$ , and their contact ion pairs to goethite (1 0 1) and (2 1 0) surfaces. The multitude of Pb(II) adsorption sites and possibility of Pb(II)-induced FeOH deprotonation make this a complex problem. At surface sites where Pb(II) is coordinated to three FeO and/or FeOH groups, and with judicious choices of FeOH surface group protonation states, the predicted Fe–Pb distances are in good agreement with EXAFS measurements. Trajectories where Pb(II) is in part coordinated to only two surface Fe–O groups exhibit larger fluctuations in Pb–O distances. Pb(II)/$${\\rm SeO}_3^{2-}$$ contact ion pairs are at least metastable on goethite (2 1 0) surfaces if the $${\\rm SeO}_3^{2-}$$ has a monodentate Se–O–Fe bond. Our DFT-based molecular dynamics calculations are a prerequisite for calculations of finite temperature equilibrium binding constants of Pb(II) and Pb(II)/$${\\rm SeO}_3^{2-}$$ ion pairs to goethite adsorption sites.« less

Self-assembly of a constitutional dynamic library of Cu(II) coordination polygons and reversible sorting by crystallization.

PubMed

Rancan, Marzio; Tessarolo, Jacopo; Zanonato, Pier Luigi; Seraglia, Roberta; Quici, Silvio; Armelao, Lidia

2013-06-07

A small coordination constitutional dynamic library (CDL) is self-assembled from Cu(2+) ions and the ortho bis-(3-acetylacetone)benzene ligand. Two coordination polygons, a rhomboid and a triangle, establish a dynamic equilibrium. Quantitative sorting of the rhomboidal polygon is reversibly obtained by crystallization. Thermodynamic and kinetic aspects ruling the CDL system have been elucidated.

Dynamic Data Driven Experiment Control Coordinated with Anisotropic Elastic Material Characterization

Treesearch

John G. Michopoulos; Tomonari Furukawa; John C. Hermanson; Samuel G. Lambrakos

2011-01-01

The goal of this paper is to propose and demonstrate a multi level design optimization approach for the coordinated determination of a material constitutive model synchronously to the design of the experimental procedure needed to acquire the necessary data. The methodology achieves both online (real-time) and offline design of optimum experiments required for...

A one-dimensional zinc(II) coordination polymer with a three-dimensional supramolecular architecture incorporating 1-[(1H-benzimidazol-2-yl)methyl]-1H-tetrazole and adipate.

PubMed

Liu, Chun Li; Huang, Qiu Ying; Meng, Xiang Ru

2016-12-01

The synthesis of coordination polymers or metal-organic frameworks (MOFs) has attracted considerable interest owing to the interesting structures and potential applications of these compounds. It is still a challenge to predict the exact structures and compositions of the final products. A new one-dimensional coordination polymer, catena-poly[[[bis{1-[(1H-benzimidazol-2-yl)methyl]-1H-tetrazole-κN 3 }zinc(II)]-μ-hexane-1,6-dicarboxylato-κ 4 O 1 ,O 1' :O 6 ,O 6' ] monohydrate], {[Zn(C 6 H 8 O 4 )(C 9 H 8 N 6 ) 2 ]·H 2 O} n , has been synthesized by the reaction of Zn(Ac) 2 (Ac is acetate) with 1-[(1H-benzimidazol-2-yl)methyl]-1H-tetrazole (bimt) and adipic acid (H 2 adi) at room temperature. In the polymer, each Zn II ion exhibits an irregular octahedral ZnN 2 O 4 coordination geometry and is coordinated by two N atoms from two symmetry-related bimt ligands and four O atoms from two symmetry-related dianionic adipate ligands. Zn II ions are connected by adipate ligands into a one-dimensional chain which runs parallel to the c axis. The bimt ligands coordinate to the Zn II ions in a monodentate mode on both sides of the main chain. In the crystal, the one-dimensional chains are further connected through N-H...O hydrogen bonds, leading to a three-dimensional supramolecular architecture. In addition, the title polymer exhibits fluorescence, with emissions at 334 and 350 nm in the solid state at room temperature.

Light driven mesoscale assembly of a coordination polymeric gelator into flowers and stars with distinct properties.

PubMed

Mukhopadhyay, Rahul Dev; Praveen, Vakayil K; Hazra, Arpan; Maji, Tapas Kumar; Ajayaghosh, Ayyappanpillai

2015-11-13

Control over the self-assembly process of porous organic-inorganic hybrids often leads to unprecedented polymorphism and properties. Herein we demonstrate how light can be a powerful tool to intervene in the kinetically controlled mesoscale self-assembly of a coordination polymeric gelator. Ultraviolet light induced coordination modulation via photoisomerisation of an azobenzene based dicarboxylate linker followed by aggregation mediated crystal growth resulted in two distinct morphological forms (flowers and stars), which show subtle differences in their physical properties.

Recent developments in the Thomson Parabola Spectrometer diagnostic for laser-driven multi-species ion sources

NASA Astrophysics Data System (ADS)

Alejo, A.; Gwynne, D.; Doria, D.; Ahmed, H.; Carroll, D. C.; Clarke, R. J.; Neely, D.; Scott, G. G.; Borghesi, M.; Kar, S.

2016-10-01

Ongoing developments in laser-driven ion acceleration warrant appropriate modifications to the standard Thomson Parabola Spectrometer (TPS) arrangement in order to match the diagnostic requirements associated to the particular and distinctive properties of laser-accelerated beams. Here we present an overview of recent developments by our group of the TPS diagnostic aimed to enhance the capability of diagnosing multi-species high-energy ion beams. In order to facilitate discrimination between ions with same Z/A, a recursive differential filtering technique was implemented at the TPS detector in order to allow only one of the overlapping ion species to reach the detector, across the entire energy range detectable by the TPS. In order to mitigate the issue of overlapping ion traces towards the higher energy part of the spectrum, an extended, trapezoidal electric plates design was envisaged, followed by its experimental demonstration. The design allows achieving high energy-resolution at high energies without sacrificing the lower energy part of the spectrum. Finally, a novel multi-pinhole TPS design is discussed, that would allow angularly resolved, complete spectral characterization of the high-energy, multi-species ion beams.

Photoactive devices including porphyrinoids with coordinating additives

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

Forrest, Stephen R; Zimmerman, Jeramy; Yu, Eric K

Coordinating additives are included in porphyrinoid-based materials to promote intermolecular organization and improve one or more photoelectric characteristics of the materials. The coordinating additives are selected from fullerene compounds and organic compounds having free electron pairs. Combinations of different coordinating additives can be used to tailor the characteristic properties of such porphyrinoid-based materials, including porphyrin oligomers. Bidentate ligands are one type of coordinating additive that can form coordination bonds with a central metal ion of two different porphyrinoid compounds to promote porphyrinoid alignment and/or pi-stacking. The coordinating additives can shift the absorption spectrum of a photoactive material toward higher wavelengths,more » increase the external quantum efficiency of the material, or both.« less

Knowledge-driven institutional change: an empirical study on combating desertification in northern China from 1949 to 2004.

PubMed

Yang, Lihua; Wu, Jianguo

2012-11-15

Understanding institutional changes is crucial for environmental management. Here we investigated how institutional changes influenced the process and result of desertification control in northern China between 1949 and 2004. Our analysis was based on a case study of 21 field sites and a meta-analysis of additional 29 sites reported in the literature. Our results show that imposed knowledge-driven institutional change was often perceived as a more progressive, scientific, and rational type of institutional change by entrepreneurs, scholars, experts, and technicians, while voluntary, knowledge-driven institutional change based on indigenous knowledge and experiences of local populations was discouraged. Our findings also demonstrate that eight working rules of imposed knowledge-driven institutional change can be applied to control desertification effectively. These rules address the issues of perception of potential gains, entrepreneurs' appeals and support, coordination of multiple goals, collaboration among multiple organizations, interest distribution and conflict resolution, incremental institutional change, external intervention, and coordination among the myriad institutions involved. Imposed knowledge-driven institutional change tended to be more successful when these rules were thoroughly implemented. These findings provide an outline for implementing future institutional changes and policy making to combat desertification and other types of ecological and environmental management. Copyright © 2012 Elsevier Ltd. All rights reserved.

Proton-driven amide bond-cleavage pathways of gas-phase peptide ions lacking mobile protons.

PubMed

Bythell, Benjamin J; Suhai, Sándor; Somogyi, Arpád; Paizs, Béla

2009-10-07

The mobile proton model (Dongre, A. R., Jones, J. L., Somogyi, A. and Wysocki, V. H. J. Am. Chem. Soc. 1996, 118 , 8365-8374) of peptide fragmentation states that the ionizing protons play a critical role in the gas-phase fragmentation of protonated peptides upon collision-induced dissociation (CID). The model distinguishes two classes of peptide ions, those with or without easily mobilizable protons. For the former class mild excitation leads to proton transfer reactions which populate amide nitrogen protonation sites. This enables facile amide bond cleavage and thus the formation of b and y sequence ions. In contrast, the latter class of peptide ions contains strongly basic functionalities which sequester the ionizing protons, thereby often hindering formation of sequence ions. Here we describe the proton-driven amide bond cleavages necessary to produce b and y ions from peptide ions lacking easily mobilizable protons. We show that this important class of peptide ions fragments by different means from those with easily mobilizable protons. We present three new amide bond cleavage mechanisms which involve salt-bridge, anhydride, and imine enol intermediates, respectively. All three new mechanisms are less energetically demanding than the classical oxazolone b(n)-y(m) pathway. These mechanisms offer an explanation for the formation of b and y ions from peptide ions with sequestered ionizing protons which are routinely fragmented in large-scale proteomics experiments.

Energetic ion losses caused by magnetohydrodynamic activity resonant and non-resonant with energetic ions in Large Helical Device

NASA Astrophysics Data System (ADS)

Ogawa, Kunihiro; Isobe, Mitsutaka; Toi, Kazuo; Shimizu, Akihiro; Spong, Donald A.; Osakabe, Masaki; Yamamoto, Satoshi; the LHD Experiment Group

2014-09-01

Experiments to reveal energetic ion dynamics associated with magnetohydrodynamic activity are ongoing in the Large Helical Device (LHD). Interactions between beam-driven toroidal Alfvén eigenmodes (TAEs) and energetic ions have been investigated. Energetic ion losses induced by beam-driven burst TAEs have been observed using a scintillator-based lost fast-ion probe (SLIP) in neutral beam-heated high β plasmas. The loss flux of co-going beam ions increases as the TAE amplitude increases. In addition to this, the expulsion of beam ions associated with edge-localized modes (ELMs) has been also recognized in LHD. The SLIP has indicated that beam ions having co-going and barely co-going orbits are affected by ELMs. The relation between ELM amplitude and ELM-induced loss has a dispersed structure. To understand the energetic ion loss process, a numerical simulation based on an orbit-following model, DELTA5D, that incorporates magnetic fluctuations is performed. The calculation result shows that energetic ions confined in the interior region are lost due to TAE instability, with a diffusive process characterizing their loss. For the ELM, energetic ions existing near the confinement/loss boundary are lost through a convective process. We found that the ELM-induced loss flux measured by SLIP changes with the ELM phase. This relation between the ELM amplitude and measured ELM-induced loss results in a more dispersed loss structure.

Faraday-cup-type lost fast ion detector on Heliotron J.

PubMed

Yamamoto, S; Ogawa, K; Isobe, M; Darrow, D S; Kobayashi, S; Nagasaki, K; Okada, H; Minami, T; Kado, S; Ohshima, S; Weir, G M; Nakamura, Y; Konoshima, S; Kemmochi, N; Ohtani, Y; Mizuuchi, T

2016-11-01

A Faraday-cup type lost-fast ion probe (FLIP) has been designed and installed in Heliotron J for the purpose of the studies of interaction between fast ions and MHD instabilities. The FLIP can measure the co-going fast ions whose energy is in the range of 1.7-42.5 keV (proton) and pitch angle of 90 ∘ -140 ∘ , especially for fast ions having the injection energy of neutral beam injection (NBI). The FLIP successfully measured the re-entering passing ions and trapped lost-fast ions caused by fast-ion-driven energetic particle modes in NBI heated plasmas.

Cation-Dependent Gold Recovery with α-Cyclodextrin Facilitated by Second-Sphere Coordination.

PubMed

Liu, Zhichang; Samanta, Avik; Lei, Juying; Sun, Junling; Wang, Yuping; Stoddart, J Fraser

2016-09-14

Herein, we report an alkali metal cation-dependent approach to gold recovery, facilitated by second-sphere coordination with eco-friendly α-cyclodextrin (α-CD). Upon mixing eight salts composed of Na(+), K(+), Rb(+), or Cs(+) cations and [AuX4](-) (X = Cl/Br) anions with α-, β-, or γ-CD in water, co-precipitates form selectively from the three (out of 24) aqueous solutions containing α-CD with KAuBr4, RbAuBr4, and CsAuBr4, from which the combination of α-CD and KAuBr4 affords the highest yield. Single-crystal X-ray analyses reveal that in 20 of the 24 adducts CD and [AuX4](-) anions form 2:1 sandwich-type second-sphere adducts driven partially by [C-H···X-Au] interactions between [AuX4](-) anions and the primary faces of two neighboring CDs. In the adduct formed between α-CD and KAuBr4, a [K(OH2)6](+) cation is encapsulated inside the cavity between the secondary faces of two α-CDs, leading to highly efficient precipitation owing to the formation of a cation/anion alternating ion wire residing inside a continuous α-CD nanotube. By contrast, in the other 19 adducts, the cations are coordinated by OH groups and glucopyranosyl ring O atoms in CDs. The strong coordination of Rb(+) and Cs(+) cations by these ligands, in conjunction with the stereoelectronically favorable binding of [AuBr4](-) anions with two α-CDs, facilitates the co-precipitation of the two adducts formed between α-CD with RbAuBr4 and CsAuBr4. In order to develop an efficient process for green gold recovery, the co-precipitation yield of α-CD and KAuBr4 has been optimized regarding both the temperature and the molar ratio of α-CD to KAuBr4.

Shear-flow trapped-ion-mode interaction revisited. II. Intermittent transport associated with low-frequency zonal flow dynamics

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

Ghizzo, A., E-mail: alain.ghizzo@univ-lorraine.fr; Palermo, F.

We address the mechanisms underlying low-frequency zonal flow generation in turbulent system and the associated intermittent regime of ion-temperature-gradient (ITG) turbulence. This model is in connection with the recent observation of quasi periodic zonal flow oscillation at a frequency close to 2 kHz, at the low-high transition, observed in the ASDEX Upgrade [Conway et al., Phys. Rev. Lett. 106, 065001 (2011)] and EAST tokamak [Xu et al., Phys. Rev. Lett 107, 125001 (2011)]. Turbulent bursts caused by the coupling of Kelvin-Helmholtz (KH) driven shear flows with trapped ion modes (TIMs) were investigated by means of reduced gyrokinetic simulations. It was foundmore » that ITG turbulence can be regulated by low-frequency meso-scale zonal flows driven by resonant collisionless trapped ion modes (CTIMs), through parametric-type scattering, a process in competition with the usual KH instability.« less

The effect of beam-driven return current instability on solar hard X-ray bursts

NASA Technical Reports Server (NTRS)

Cromwell, D.; Mcquillan, P.; Brown, J. C.

1986-01-01

The problem of electrostatic wave generation by a return current driven by a small area electron beam during solar hard X-ray bursts is discussed. The marginal stability method is used to solve numerically the electron and ion heating equations for a prescribed beam current evolution. When ion-acoustic waves are considered, the method appears satisfactory and, following an initial phase of Coulomb resistivity in which T sub e/T sub i rise, predicts a rapid heating of substantial plasma volumes by anomalous ohmic dissipation. This hot plasma emits so much thermal bremsstrahlung that, contrary to previous expectations, the unstable beam-plasma system actually emits more hard X-rays than does the beam in the purely collisional thick target regime relevant to larger injection areas. Inclusion of ion-cyclotron waves results in ion-acoustic wave onset at lower T sub e/T sub i and a marginal stability treatment yields unphysical results.

Status of the RF-driven H{sup −} ion source for J-PARC linac

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

Oguri, H., E-mail: oguri.hidetomo@jaea.go.jp; Ohkoshi, K.; Ikegami, K.

2016-02-15

For the upgrade of the Japan Proton Accelerator Research Complex linac beam current, a cesiated RF-driven negative hydrogen ion source was installed during the 2014 summer shutdown period, with subsequent operations commencing on September 29, 2014. The ion source has been successfully operating with a beam current and duty factor of 33 mA and 1.25% (500 μs and 25 Hz), respectively. The result of recent beam operation has demonstrated that the ion source is capable of continuous operation for approximately 1100 h. The spark rate at the beam extractor was observed to be at a frequency of less than oncemore » a day, which is an acceptable level for user operation. Although an antenna failure occurred during operation on October 26, 2014, no subsequent serious issues have occurred since then.« less

Waves and instabilities in high β, warm ion plasmas in LAPD

NASA Astrophysics Data System (ADS)

Carter, T. A.; Dorfman, S. E.; Rossi, G.; Guice, D.

2014-12-01

The LArge Plasma Device (LAPD) has been upgraded with a second LaB6 cathode plasma source that permits the creation of higher density (~ 3×1013 cm-3), higher temperature (Te ~ 12eV), warm ion (Ti ~ 6eV) plasmas. Along with lowered magnetic field, significant increases in plasma β can be achieved with this new source (e.g. at B=100G, β~1). These new plasma conditions permit a range of new experimental opportunities on LAPD including: linear and nonlinear studies of Alfvén waves in warm ion, high β plasmas; pressure-gradient driven instabilities in increased β plasmas and electromagnetic modifications to turbulence and transport; instabilities driven by ion temperature anisotropies (e.g. firehose and mirror instabilities). The characteristics of the new plasma will be presented along with a discussion of these new research areas.

Waves and instabilities in high β, warm ion plasmas in LAPD

NASA Astrophysics Data System (ADS)

Carter, Troy; Dorfman, Seth; Rossi, Giovanni; Guice, Daniel; Gekelman, Walter; Klein, Kris; Howes, Greg

2014-10-01

The LArge Plasma Device (LAPD) has been upgraded with a second LaB6 cathode plasma source that permits the creation of higher density (~ 3 ×1013 cm-3), higher temperature (Te ~ 12 eV), warm ion (Ti ~ 6 eV) plasmas. Along with lowered magnetic field, significant increases in plasma β can be achieved with this new source (e.g. at B = 100 G , β ~ 1). These new plasma conditions permit a range of new experimental opportunities on LAPD including: linear and nonlinear studies of Alfvén waves in warm ion, high β plasmas; pressure-gradient driven instabilities in increased β plasmas and electromagnetic modifications to turbulence and transport; instabilities driven by ion temperature anisotropies (e.g. firehose and mirror instabilities). The characteristics of the new plasma will be presented along with a discussion of these new research areas.

Electromagnetic ion cyclotron waves in the plasma depletion layer

NASA Technical Reports Server (NTRS)

Denton, Richard E.; Hudson, Mary K.; Fuselier, Stephen A.; Anderson, Brian J.

1993-01-01

Results of a study of the theoretical properties of electromagnetic ion cyclotron (EMIC) waves which occur in the plasma depletion layer are presented. The analysis assumes a homogeneous plasma with the characteristics which were measured by the AMPTE/CCE satellite at 1450-1501 UT on October 5, 1984. Waves were observed in the Pc 1 frequency range below the hydrogen gyrofrequency, and these waves are identified as EMIC waves. The higher-frequency instability is driven by the temperature anisotropy of the H(+) ions, while the lower-frequency instability is driven by the temperature anisotropy of the He(2+) ions. It is argued that the higher-frequency waves will have k roughly parallel to B(0) and will be left-hand polarized, while the lower frequency wave band will have k oblique to B(0) and will be linearly polarized, in agreement with observations.

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

Jin, Xin; Zhou, Pei; Zheng, Chunying

A copper complex ([Cu(py){sub 2}(L){sub 2}]·2CH{sub 3}OH){sub n} (HL=(E)-3-(3-hydroxyl-phenyl)-acrylic acid) (1) with acrylic acid ligand was synthesized and structurally analyzed by IR, elemental analysis, TGA and the single-crystal X-ray diffraction methods. It is the first time to find that phenolic hydroxyl of L coordinates to Cu(II). Complex 1 exhibits 1D chain by a double-bridge of ligands, and the 3D supramolecular framework in complex 1 is constructed by π–π stacking interactions and van der Waals Contacts among the 1D chains. The magnetic properties of complex 1 have been studied. - Graphical abstract: A copper complex based on (E)-3-(3-hydroxyl-phenyl)-acrylic acid in amore » novel coordinated way was synthesized and a ferromagnetic exchange interactions between neighboring Cu(II) ions has be achieved. - Highlights: • A new copper complex with acrylic acid ligand was synthesized and analyzed. • We find the phenolic hydroxyl of MCA ligand coordinates to metal ion firstly. • A ferromagnetic exchange interactions between Cu(II) ions has been achieved.« less

Development of a compact, rf-driven, pulsed ion source for neutron generation

NASA Astrophysics Data System (ADS)

Perkins, L. T.; Celata, C.; Lee, Y.; Leung, K. N.; Picard, D. S.; Vilaithong, R.; Williams, M. D.; Wutte, D.

1997-02-01

Lawrence Berkeley National Laboratory is currently developing a compact, sealed-accelerator-tube neutron generator capable of producing a neutron flux in the range of 109 to 1010 D-T neutrons per second. The ion source, a miniaturized variation of earlier radio-frequency (rf)-driven multicusp ion sources, is designed to fit within a ˜5 cm diameter borehole. Typical operating parameters include repetition rates up to 100 pps, with pulse widths between 10 and 80 μs (limited only by the available rf power supply) and source pressures as low as ˜5 mTorr. In this configuration, peak extractable hydrogen current densities exceeding 1180 mA/cm2 with H1+ yields over 94% having been achieved.

Di-μ3-chlorido-tetra-μ2-chlorido-dichloridobis(dimethyl­formamide-κO)hexa­kis­(1H-imidazole-κN 3)tetra­cadmium

PubMed Central

Zhu, Run-Qiang

2011-01-01

The centrosymmetric mol­ecule of the title complex, [Cd4Cl8(C3H4N2)6(C3H7NO)2], contains four CdII atoms, six imidazole, two dimethyl­formamide and eight chloride ligands. The structure shows a novel chloride-bridged tetra­nuclear cadmium quasi-cubane cluster. The coordination geometry of all CdII atoms is distorted octa­hedral, with the two metal atoms in the asymmetric unit in different coordination environments. One of the Cd2+ ions is coordinated by five Cl− ions and by one N atom from an imidazole ligand, while the second is coordinated by three chloride ligands, two N atoms from two imidazole ligands and one O atom from a dimethyl­formamide mol­ecule. Inter­molecular N—H⋯Cl hydrogen bonds link the mol­ecules into a two-dimensional polymeric structure parallel to the ab plane. PMID:22058708

NO3- Coordination in Aqueous Solutions by 15N/ 14N and 18O/natO Isotopic Substitution: What Can We Learn from Molecular Simulation?

DOE PAGES

Chialvo, Ariel A.; Vlcek, Lukas

2014-12-16

We explore the deconvolution of the water-nitrate correlations by the first-order difference approach involving neutron diffraction of heavy- and null-aqueous solutions of KNO 3 under 14N 15N and natON 18ON substitutions to achieve a full characterization of the first water coordination around the nitrate ion. For that purpose we performed isobaric-isothermal simulations of 3.5m KNO 3 aqueous solutions at ambient conditions to generate the relevant radial distribution functions (RDF) required in the analysis (a) to identify the individual partial contributions to the total neutron weighted distribution function, (b) to isolate and assess the contribution of NO 3 -!K + pairmore » formation, (c) to test the accuracy of the NDIS-based coordination calculations and XRDbased assumptions, and (d) to describe the water coordination around both the nitrogen and oxygen sites of the nitrate ion.« less

Syntheses and structural characterization of Co(II) and Cd(II) coordination polymers with 1,4-bis(imidazolyl)butane ligand

NASA Astrophysics Data System (ADS)

Lalegani, Arash; Khalaj, Mehdi; Sedaghat, Sajjad; Łyczko, Krzysztof; Lipkowski, Janusz

2017-11-01

Two new coordination polymers, {[Co(bib)3](PF6)2}n (1) and [Cd (bib) Cl2]n (2), were prepared at room temperature by the reaction of appropriate salts of cobalt (II) and cadmium (II) with the flexible linker ligands 1,4-bis(imidazolyl) butane (bib). The compounds were characterized by elemental analyses, IR spectroscopy and single crystal X-ray diffraction. In the polymeric structure of 1, the Co(II) ion lies on an inversion centre and adopts the CoN6 octahedral geometry, while in the structure of 2, the Cd(II) ions adopt the CdN2Cl4 pseudo-octahedral geometry. In compound 1, six bib ligands are coordinated to one central cobalt (II) to form an open 3D 2-fold interpenetrating framework of the α-polonium (pcu) type topology, while in compound 2 two bib ligands are coordinated to one central cadmium (II) to form 2D network structure.

Structural diversity of alkaline-earth 2,5-thiophenedicarboxylates

NASA Astrophysics Data System (ADS)

Balendra; Ramanan, Arunachalam

2017-03-01

Exploration of the structural landscape of the system containing divalent alkaline-earth metal ion (Mg, Ca and Sr) with the rigid 2,5-thiophenedicarboxylic acid (TDC) under varying solvothermal condition (DMF, DMA and DEF) yielded five new crystals: [Mg(TDC) (DEF)2(H2O)1/2] (1), [Ca(TDC) (DMA)] (2), [Ca(TDC) (DMA) (H2O)] (3), [Sr(TDC) (DMA)] (4) and [Sr(TDC) (DMA) (H2O)] (5) and two known solids. Single crystal structures of all the solids are characteristic of extended coordination interaction between metal and carboxylate ions. While the smaller magnesium ion crystallized into a 2D coordination polymer, the larger calcium and strontium compounds resulted into the growth of 3D metal organic frameworks. All the solids show blue emission arising from intra ligand charge transfer.

Hydrothermal syntheses, characterizations and crystal structures of a new lead(II) carboxylate-phosphonate with a double layer structure and a new nickel(II) carboxylate-phosphonate containing a hydrogen-bonded 2D layer with intercalation of ethylenediamines

NASA Astrophysics Data System (ADS)

Song, Jun-Ling; Mao, Jiang-Gao; Sun, Yan-Qiong; Zeng, Hui-Yi; Kremer, Reinhard K.; Clearfield, Abraham

2004-03-01

Hydrothermal reactions of N, N-bis(phosphonomethyl)aminoacetic acid (HO 2CCH 2N(CH 2PO 3H 2) 2) with metal(II) salts afforded two new metal carboxylate-phosphonates, namely, Pb 2[O 2CCH 2N(CH 2PO 3)(CH 2PO 3H)]·H 2O ( 1) and {NH 3CH 2CH 2NH 3}{Ni[O 2CCH 2N(CH 2PO 3H) 2](H 2O) 2} 2 ( 2). Among two unique lead(II) ions in the asymmetric unit of complex 1, one is five coordinated by five phosphonate oxygen atoms from 5 ligands, whereas the other one is five-coordinated by a tridentate chelating ligand (1 N and 2 phosphonate O atoms) and two phosphonate oxygen atoms from two other ligands. The carboxylate group of the ligand remains non-coordinated. The bridging of above two types of lead(II) ions through phosphonate groups resulted in a <002> double layer with the carboxylate group of the ligand as a pendant group. These double layers are further interlinked via hydrogen bonds between the carboxylate groups into a 3D network. The nickel(II) ion in complex 2 is octahedrally coordinated by a tetradentate chelating ligand (two phosphonate oxygen atoms, one nitrogen and one carboxylate oxygen atoms) and two aqua ligands. These {Ni[O 2CCH 2N(CH 2PO 3H) 2][H 2O] 2} - anions are further interlinked via hydrogen bonds between non-coordinated phosphonate oxygen atoms to form a <800> hydrogen bonded 2D layer. The 2H-protonated ethylenediamine cations are intercalated between two layers, forming hydrogen bonds with the non-coordinated carboxylate oxygen atoms. Results of magnetic measurements for complex 2 indicate that there is weak Curie-Weiss behavior with θ=-4.4 K indicating predominant antiferromagnetic interaction between the Ni(II) ions. Indication for magnetic low-dimension magnetism could not be detected.

RF absorption and ion heating in helicon sources.

PubMed

Kline, J L; Scime, E E; Boivin, R F; Keesee, A M; Sun, X; Mikhailenko, V S

2002-05-13

Experimental data are presented that are consistent with the hypothesis that anomalous rf absorption in helicon sources is due to electron scattering arising from parametrically driven ion-acoustic waves downstream from the antenna. Also presented are ion temperature measurements demonstrating anisotropic heating (T( perpendicular)>T(parallel)) at the edge of the discharge. The most likely explanation is ion-Landau damping of electrostatic slow waves at a local lower-hybrid-frequency resonance.

Waves and Instabilities in Collisionless Shocks

DTIC Science & Technology

1984-04-01

occur in the electron foreshock and are driven by suprathermal electrons escaping into the region upstream of the shock. Both the ion-acoustic and...ULF waves occur in the ion foreshock and are associated with ions streaming into the region upstream of 11 the shock. The region downstream of the...the discussion of these waves it is useful to distinguish two regions, called the electron foreshock and the ion foreshock . Because the particles

Stabilization of sawteeth with third harmonic deuterium ICRF-accelerated beam in JET plasmas

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

Girardo, Jean-Baptiste; CEA, IRFM, F-13108 Saint-Paul-lez-Durance; Sharapov, Sergei

Sawtooth stabilisation by fast ions is investigated in deuterium (D) and D-helium 3 (He3) plasmas of JET heated by deuterium Neutral Beam Injection combined in synergy with Ion Cyclotron Resonance Heating (ICRH) applied on-axis at 3rd beam cyclotron harmonic. A very significant increase in the sawtooth period is observed, caused by the ICRH-acceleration of the beam ions born at 100 keV to the MeV energy range. Four representative sawteeth from four different discharges are compared with Porcelli's model. In two discharges, the sawtooth crash appears to be triggered by core-localized Toroidal Alfvén Eigenmodes inside the q = 1 surface (also called “tornado” modes)more » which expel the fast ions from within the q = 1 surface, over time scales comparable with the sawtooth period. Two other discharges did not exhibit fast ion-driven instabilities in the plasma core, and no degradation of fast ion confinement was found in both modelling and direct measurements of fast ion profile with the neutron camera. The developed sawtooth scenario without fast ion-driven instabilities in the plasma core is of high interest for the burning plasmas. Possible causes of the sawtooth crashes on JET are discussed.« less

Field-driven ion migration against dead-stop collisional braking

NASA Astrophysics Data System (ADS)

Grzesik, J. A.

1988-02-01

The steady-state migration of ions, driven by a uniform electric field against full-stop collisions, is investigated in some detail. The required phase-space distribution is obtained very easily from Boltzmann's equation together with explicit recognition of energy conservation and population balance for the stagnant ion pool. We go on to decompose this aggregate solution into ion tiers classified by the number of background impacts previously endured. Such a decomposition permits us to detect the presence of Poisson statistics (as to collision number) lurking within the composite, thermalized Maxwellian, and likewise also a multiple-scattering hierarchy having the maiden, first-flight distribution for its natural kernel. Scattering-sequence accounting, in particular, allows a quantitative (even though unwieldy) distinction to be made between ions of varying residence times. A model of this sort is motivated by the technique of ion implantation through sample immersion within a plasma at higher electric potential. Numerical consequences of the solution obtained here reveal that both ion density and average kinetic energy relax to their terminal values within just a few mean free-path lengths. Such modest scaling of plasma-sheath extent evidently carries a beneficial implication for the technological ease with which surface properties (such as metal corrosion resistance and hardness) remain open to improvement via ion bombardment.

Intelligent multiagent coordination based on reinforcement hierarchical neuro-fuzzy models.

PubMed

Mendoza, Leonardo Forero; Vellasco, Marley; Figueiredo, Karla

2014-12-01

This paper presents the research and development of two hybrid neuro-fuzzy models for the hierarchical coordination of multiple intelligent agents. The main objective of the models is to have multiple agents interact intelligently with each other in complex systems. We developed two new models of coordination for intelligent multiagent systems, which integrates the Reinforcement Learning Hierarchical Neuro-Fuzzy model with two proposed coordination mechanisms: the MultiAgent Reinforcement Learning Hierarchical Neuro-Fuzzy with a market-driven coordination mechanism (MA-RL-HNFP-MD) and the MultiAgent Reinforcement Learning Hierarchical Neuro-Fuzzy with graph coordination (MA-RL-HNFP-CG). In order to evaluate the proposed models and verify the contribution of the proposed coordination mechanisms, two multiagent benchmark applications were developed: the pursuit game and the robot soccer simulation. The results obtained demonstrated that the proposed coordination mechanisms greatly improve the performance of the multiagent system when compared with other strategies.

Phosphorus-supported ligands for the assembly of multimetal architectures.

PubMed

Chandrasekhar, Vadapalli; Murugesapandian, Balasubramanian

2009-08-18

Modeled after boron-based scorpionate ligands, acyclic and cyclic phosphorus-containing compounds possessing reactive groups can serve as excellent precursors for the assembly of novel phosphorus-supported ligands that can coordinate multiple sites. In such ligands, the phosphorus atom does not have any role in coordination but is used as a structural support to assemble one or more coordination platforms. In this Account, we describe the utility of inorganic heterocyclic rings such as cyclophosphazenes and carbophosphazenes as well as acyclic phosphorus-containing compounds such as (S)PCl(3), RP(O)Cl(2), and R(2)P(O)Cl for building such multisite coordination platforms. We can modulate the number and orientation of such coordination platforms through the choice of the phosphorus-containing precursor. This methodology is quite general and modular and allows the creation of well-defined libraries of multisite coordination ligands. Phosphorus-supported pyrazolyl ligands are quite useful for building multimetallic architectures. Some of these ligands are prone to P-N bond hydrolysis upon metalation, but we have exploited the P-N bond sensitivity to generate hydrolyzed ligands in situ, which are useful to build multimetal assemblies. In addition, the intimate relationship between small molecule cyclophosphazenes and the corresponding pendant cyclophosphazene-containing polymer systems facilitated our design of polymer-supported catalysts for phosphate ester hydrolysis, plasmid DNA modification, and C-C bond formation reactions. Phosphorus hydrazides containing reactive amine groups are ideal precursors for integration into more complex ligand systems. The ligand (S)P[N(Me)N=CH-C(6)H(4)-2-OH](3) (LH(3)) contains six coordination sites, and its coordination response depends upon the oxidation state of the metal ion employed. LH(3) reacts with divalent transition metal ions to afford neutral trimetallic derivatives L(2)M(3), where the three metal ions are arranged in a perfectly linear manner in many cases. Incorporating an additional methoxy group into LH(3) affords the ligand (S)P[N(Me)N=CH-C(6)H(3)-2-OH-3-OMe](3) (L'H(3)), which contains nine coordination sites: three imino nitrogen atoms, three phenolate oxygen atoms, and three methoxy oxygen atoms. The reaction of L'H(3) with transition metal salts in 1:1 ratio leads to the in situ formation of a metalloligand (L'M), which on further treatment with lanthanide salts gives heterobimetallic trinuclear cationic complexes [L'(2)M(2)Ln](+) containing a M-Ln-M linear array (M = transition metal ion in a +2 oxidation state). Many of these 3d-4f compounds behave as single-molecule magnets at low temperatures. Although challenges remain in the development of synthetic methods and in the architectural control of the coordination platforms, we see opportunities for further research into coordination platforms supported by main group elements such as phosphorus. As we have shown in this Account, one potential disadvantage, sensitivity of P-N bonds to hydrolysis, can be used successfully to build larger assemblies.

Synthesis and characterization of the tetranuclear iron(III) complex of a new asymmetric multidentate ligand. A structural model for purple acid phosphatases.

PubMed

Boudalis, Athanassios K; Aston, Robyn E; Smith, Sarah J; Mirams, Ruth E; Riley, Mark J; Schenk, Gerhard; Blackman, Allan G; Hanton, Lyall R; Gahan, Lawrence R

2007-11-28

The ligand, 2-((2-hydroxy-5-methyl-3-((pyridin-2-ylmethylamino)methyl)benzyl)(2-hydroxybenzyl)amino)acetic acid (H(3)HPBA), which contains a donor atom set that mimics that of the active site of purple acid phosphatase is described. Reaction of H(3)HPBA with iron(III) or iron(II) salts results in formation of the tetranuclear complex, [Fe(4)(HPBA)(2)(OAc)(2)(mu-O)(mu-OH)(OH(2))(2)]ClO(4) x 5H(2)O. X-Ray structural analysis reveals the cation consists of four iron(III) ions, two HPBA(3-) ligands, two bridging acetate ligands, a bridging oxide ion and a bridging hydroxide ion. Each binucleating HPBA(3-) ligand coordinates two structurally distinct hexacoordinate iron(III) ions. The two metal ions coordinated to a HPBA(3-) ligand are linked to the two iron(III) metal ions of a second, similar binuclear unit by intramolecular oxide and hydroxide bridging moieties to form a tetramer. The complex has been further characterised by elemental analysis, mass spectrometry, UV-vis and MCD spectroscopy, X-ray crystallography, magnetic susceptibility measurements and variable-temperature Mössbauer spectroscopy.

Need for reaction coordinates to ensure a complete basis set in an adiabatic representation of ion-atom collisions

NASA Astrophysics Data System (ADS)

Rabli, Djamal; McCarroll, Ronald

2018-02-01

This review surveys the different theoretical approaches, used to describe inelastic and rearrangement processes in collisions involving atoms and ions. For a range of energies from a few meV up to about 1 keV, the adiabatic representation is expected to be valid and under these conditions, inelastic and rearrangement processes take place via a network of avoided crossings of the potential energy curves of the collision system. In general, such avoided crossings are finite in number. The non-adiabatic coupling, due to the breakdown of the Born-Oppenheimer separation of the electronic and nuclear variables, depends on the ratio of the electron mass to the nuclear mass terms in the total Hamiltonian. By limiting terms in the total Hamiltonian correct to first order in the electron to nuclear mass ratio, a system of reaction coordinates is found which allows for a correct description of both inelastic channels. The connection between the use of reaction coordinates in the quantum description and the electron translation factors of the impact parameter approach is established. A major result is that only when reaction coordinates are used, is it possible to introduce the notion of a minimal basis set. Such a set must include all avoided crossings including both radial coupling and long range Coriolis coupling. But, only when reactive coordinates are used, can such a basis set be considered as complete. In particular when the centre of nuclear mass is used as centre of coordinates, rather than the correct reaction coordinates, it is shown that erroneous results are obtained. A few results to illustrate this important point are presented: one concerning a simple two-state Landau-Zener type avoided crossing, the other concerning a network of multiple crossings in a typical electron capture process involving a highly charged ion with a neutral atom.

Syntheses, structures and properties of four 3D microporous lanthanide coordination polymers based on 3,5-pyrazoledicarboxylate and oxalate ligands

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

Song, Juan; Wang, Ji-Jiang; Hu, Huai-Ming, E-mail: ChemHu1@NWU.EDU.CN

2014-04-01

Four three-dimensional lanthanide coordination polymers with reversible structural interconversions, [Ln{sub 2}(Hpdc){sub 2}(C{sub 2}O{sub 4})(H{sub 2}O){sub 4}]{sub n}·2nH{sub 2}O [Ln=Sm (1), Eu (2), Tb (3) and Dy (4)], have been synthesized by hydrothermal reactions of lanthanide nitrates with 3,5-pyrazoledicarboxylic (H{sub 3}pdc) and oxalic acids. It is noteworthy that there is an in situ reaction in 1, in which H{sub 3}pdc was decomposed into (ox){sup 2−} with Cu(II)–Sm(III) synergistic effect under hydrothermal conditions. These compounds are isostructural and crystallized in the monoclinic P2{sub 1}/c space group. The Ln(III) ions are eight-coordinated with dodecahedron coordination geometry. These polyhedra are linked by oxalate groupsmore » to form 1D zigzag chain, which are further connected by 3,5-pyrazoledicarboxylate to extend similar 3D frameworks with channels along c-axis in 1–4. These coordination polymers display the characteristic emission bands of the Ln(III) ions in the solid state and possess good thermal stabilities. - Graphical abstract: Four 3D microporous lanthanide coordination polymers with reversible structural interconversion have been synthesized. They exhibit characteristic emission bands of the lanthanide ions and possess great thermal stability. - Highlights: • Four lanthanide coordination polymers have been hydrothermal synthesized. • There is an in situ reaction in 1 in which H{sub 3}pdc was decomposed into (ox){sup 2−} with the Cu(II)–Sm(III) synergistic effect under hydrothermal conditions. • TGA and XRD studies reveal that upon hydration–dehydration, compounds 1–4 undergo a reversible structural interconversion process through a cooling-heating cycle. • Compounds 1–4 exhibit characteristic lanthanide-centered luminescence.« less

Distinct dissociation kinetics between ion pairs: Solvent-coordinate free-energy landscape analysis.

PubMed

Yonetani, Yoshiteru

2015-07-28

Different ion pairs exhibit different dissociation kinetics; however, while the nature of this process is vital for understanding various molecular systems, the underlying mechanism remains unclear. In this study, to examine the origin of different kinetic rate constants for this process, molecular dynamics simulations were conducted for LiCl, NaCl, KCl, and CsCl in water. The results showed substantial differences in dissociation rate constant, following the trend kLiCl < kNaCl < kKCl < kCsCl. Analysis of the free-energy landscape with a solvent reaction coordinate and subsequent rate component analysis showed that the differences in these rate constants arose predominantly from the variation in solvent-state distribution between the ion pairs. The formation of a water-bridging configuration, in which the water molecule binds to an anion and a cation simultaneously, was identified as a key step in this process: water-bridge formation lowers the related dissociation free-energy barrier, thereby increasing the probability of ion-pair dissociation. Consequently, a higher probability of water-bridge formation leads to a higher ion-pair dissociation rate.

Hexakis(N,N-dimethyl­formamide-κO)cobalt(II) bis­(perchlorate)

PubMed Central

Eissmann, Frank; Böhle, Tony; Mertens, Florian O. R. L.; Weber, Edwin

2010-01-01

The asymmetric unit of the title complex, [Co(DMF)6](ClO4)2 (DMF = N,N-dimethyl­formamide, C3H7NO), consists of two half complex cations with the Co2+ metal ions located on centers of inversion and two perchlorate anions. In the crystal packing, each Co2+ ion is coordinated by six mol­ecules of DMF in a slightly distorted octa­hedral geometry. The crystal structure is mainly stabilized by coordinative, ionic and C—H⋯O hydrogen-bonding inter­actions. PMID:21580225

A six-coordinate ytterbium complex exhibiting easy-plane anisotropy and field-induced single-ion magnet behavior.

PubMed

Liu, Jun-Liang; Yuan, Kang; Leng, Ji-Dong; Ungur, Liviu; Wernsdorfer, Wolfgang; Guo, Fu-Sheng; Chibotaru, Liviu F; Tong, Ming-Liang

2012-08-06

The field-induced blockage of magnetization behavior was first observed in an Yb(III)-based molecule with a trigonally distorted octahedral coordination environment. Ab initio calculations and micro-SQUID measurements were performed to demonstrate the exhibition of easy-plane anisotropy, suggesting the investigated complex is the first pure lanthanide field-induced single-ion magnet (field-induced SIM) of this type. Furthermore, we found the relaxation time obeys a power law instead of an exponential law, indicating that the relaxation process should be involved a direct process rather than an Orbach process.

A Multicusp Ion Source for Radioactive Ion Beams

NASA Astrophysics Data System (ADS)

Wutte, D.; Freedman, S.; Gough, R.; Lee, Y.; Leitner, M.; Leung, K. N.; Lyneis, C.; Picard, D. S.; Sun, L.; Williams, M. D.; Xie, Z. Q.

1997-05-01

In order to produce a radioactive ion beam of (14)O+, a 10-cm-diameter, 13.56 MHz radio frequency (rf) driven multicusp ion source is now being developed at Lawrence Berkeley National Laboratory. In this paper we describe the specific ion source design and the basic ion source characteristics using Ar, Xe and a 90types of measurements have been performed: extractable ion current, ion species distributions, gas efficiency, axial energy spread and ion beam emittance measurements. The source can generate ion current densities of approximately 60 mA/cm2 . In addition the design of the ion beam extraction/transport system for the actual experimental setup for the radioactive beam line will be presented.

Bridging the Gap Between Theory and Experiment to Derive a Detailed Understanding of Hammerhead Ribozyme Catalysis

PubMed Central

Lee, Tai-Sung; Wong, Kin-Yiu; Giambasu, George M.; York, Darrin M.

2016-01-01

Herein we summarize our progress toward the understanding of hammerhead ribozyme (HHR) catalysis through a multiscale simulation strategy. Simulation results collectively paint a picture of HHR catalysis: HHR first folds to form an electronegative active site pocket to recruit a threshold occupation of cationic charges, either a Mg2+ ion or multiple monovalent cations. Catalytically active conformations that have good in-line fitness are supported by specific metal ion coordination patterns that involve either a bridging Mg2+ ion or multiple Na+ ions, one of which is also in a bridging coordination pattern. In the case of a single Mg2+ ion bound in the active site, the Mg2+ ion undergoes a migration that is coupled with deprotonation of the nucleophile (C17:O2′). As the reaction proceeds, the Mg2+ ion stabilizes the accumulating charge of the leaving group and significantly increases the general acid ability of G8:O2′. Further computational mutagenesis simulations suggest that the disruptions due to mutations may severely impact HHR catalysis at different stages of the reaction. Catalytic mechanisms supported by the simulation results are consistent with available structural and biochemical experiments, and together they advance our understanding of HHR catalysis. PMID:24156941

Spontaneous aggregation of lithium ion coordination polymers in fluorinated electrolytes for high-voltage batteries

DOE PAGES

Malliakas, Christos D.; Leung, Kevin; Pupek, Krzysztof Z.; ...

2016-03-31

Fluorinated carbonate solvents are pursued as liquid electrolytes for high-voltage Li-ion batteries. We report aggregation of [Li +(FEC) 3] n polymer species from fluoroethylene carbonate containing electrolytes and scrutinized the causes for this behavior.

Driven waves in a two-fluid plasma

NASA Astrophysics Data System (ADS)

Roberge, W. G.; Ciolek, Glenn E.

2007-12-01

We study the physics of wave propagation in a weakly ionized plasma, as it applies to the formation of multifluid, magnetohydrodynamics (MHD) shock waves. We model the plasma as separate charged and neutral fluids which are coupled by ion-neutral friction. At times much less than the ion-neutral drag time, the fluids are decoupled and so evolve independently. At later times, the evolution is determined by the large inertial mismatch between the charged and neutral particles. The neutral flow continues to evolve independently; the charged flow is driven by and slaved to the neutral flow by friction. We calculate this driven flow analytically by considering the special but realistic case where the charged fluid obeys linearized equations of motion. We carry out an extensive analysis of linear, driven, MHD waves. The physics of driven MHD waves is embodied in certain Green functions which describe wave propagation on short time-scales, ambipolar diffusion on long time-scales and transitional behaviour at intermediate times. By way of illustration, we give an approximate solution for the formation of a multifluid shock during the collision of two identical interstellar clouds. The collision produces forward and reverse J shocks in the neutral fluid and a transient in the charged fluid. The latter rapidly evolves into a pair of magnetic precursors on the J shocks, wherein the ions undergo force-free motion and the magnetic field grows monotonically with time. The flow appears to be self-similar at the time when linear analysis ceases to be valid.

Note: Ion source design for ion trap systems

NASA Astrophysics Data System (ADS)

Noriega, J. R.; Quevedo, M.; Gnade, B.; Vasselli, J.

2013-06-01

A small plasma (glow discharge) based ion source and circuit are described in this work. The ion source works by producing a high voltage pulsed discharge between two electrodes in a pressure range of 50-100 mTorr. A third mesh electrode is used for ion extraction. The electrodes are small stainless steel screws mounted in a MACOR ionization chamber in a linear arrangement. The electrode arrangement is driven by a circuit, design for low power operation. This design is a proof of concept intended for applications on small cylindrical ion traps.

Gamma source for active interrogation

DOEpatents

Leung, Ka-Ngo; Lou, Tak Pui; Barletta, William A.

2012-10-02

A cylindrical gamma generator includes a coaxial RF-driven plasma ion source and target. A hydrogen plasma is produced by RF excitation in a cylindrical plasma ion generator using an RF antenna. A cylindrical gamma generating target is coaxial with the ion generator, separated by plasma and extraction electrodes which has many openings. The plasma generator emanates ions radially over 360.degree. and the cylindrical target is thus irradiated by ions over its entire circumference. The plasma generator and target may be as long as desired.

Gamma source for active interrogation

DOEpatents

Leung, Ka-Ngo [Hercules, CA; Lou, Tak Pui [Berkeley, CA; Barletta, William A [Oakland, CA

2009-09-29

A cylindrical gamma generator includes a coaxial RF-driven plasma ion source and target. A hydrogen plasma is produced by RF excitation in a cylindrical plasma ion generator using an RF antenna. A cylindrical gamma generating target is coaxial with the ion generator, separated by plasma and extraction electrodes which has many openings. The plasma generator emanates ions radially over 360.degree. and the cylindrical target is thus irradiated by ions over its entire circumference. The plasma generator and target may be as long as desired.

Non-Native Metal Ion Reveals the Role of Electrostatics in Synaptotagmin 1-Membrane Interactions.

PubMed

Katti, Sachin; Nyenhuis, Sarah B; Her, Bin; Srivastava, Atul K; Taylor, Alexander B; Hart, P John; Cafiso, David S; Igumenova, Tatyana I

2017-06-27

C2 domains are independently folded modules that often target their host proteins to anionic membranes in a Ca 2+ -dependent manner. In these cases, membrane association is triggered by Ca 2+ binding to the negatively charged loop region of the C2 domain. Here, we used a non-native metal ion, Cd 2+ , in lieu of Ca 2+ to gain insight into the contributions made by long-range Coulombic interactions and direct metal ion-lipid bridging to membrane binding. Using X-ray crystallography, NMR, Förster resonance energy transfer, and vesicle cosedimentation assays, we demonstrate that, although Cd 2+ binds to the loop region of C2A/B domains of synaptotagmin 1 with high affinity, long-range Coulombic interactions are too weak to support membrane binding of individual domains. We attribute this behavior to two factors: the stoichiometry of Cd 2+ binding to the loop regions of the C2A and C2B domains and the impaired ability of Cd 2+ to directly coordinate the lipids. In contrast, electron paramagnetic resonance experiments revealed that Cd 2+ does support membrane binding of the C2 domains in full-length synaptotagmin 1, where the high local lipid concentrations that result from membrane tethering can partially compensate for lack of a full complement of divalent metal ions and specific lipid coordination in Cd 2+ -complexed C2A/B domains. Our data suggest that long-range Coulombic interactions alone can drive the initial association of C2A/B with anionic membranes and that Ca 2+ further augments membrane binding by the formation of metal ion-lipid coordination bonds and additional Ca 2+ ion binding to the C2 domain loop regions.

The second Cu(II)-binding site in a proton-rich environment interferes with the aggregation of amyloid-beta(1-40) into amyloid fibrils.

PubMed

Jun, Sangmi; Gillespie, Joel R; Shin, Byong-kyu; Saxena, Sunil

2009-11-17

The overall morphology and Cu(II) ion coordination for the aggregated amyloid-beta(1-40) [Abeta(1-40)] in N-ethylmorpholine (NEM) buffer are affected by Cu(II) ion concentration. This effect is investigated by transmission electron microscopy (TEM), atomic force microscopy (AFM), and electron spin echo envelope modulation (ESEEM) spectroscopy. At lower than equimolar concentrations of Cu(II) ions, fibrillar aggregates of Abeta(1-40) are observed. At these concentrations of Cu(II), the monomeric and fibrillar Abeta(1-40) ESEEM data indicate that the Cu(II) ion is coordinated by histidine residues. For aggregated Abeta(1-40) at a Cu(II):Abeta molar ratio of 2:1, TEM and AFM images show both linear fibrils and granular amorphous aggregates. The ESEEM spectra show that the multi-histidine coordination for Cu(II) ion partially breaks up and becomes exposed to water or exchangeable protons of the peptide at a higher Cu(II) concentration. Since the continuous-wave electron spin resonance results also suggest two copper-binding sites in Abeta(1-40), the proton ESEEM peak may arise from the second copper-binding site, which may be significantly involved in the formation of granular amorphous aggregates. Thioflavin T fluorescence and circular dichroism experiments also show that Cu(II) inhibits the formation of fibrils and induces a nonfibrillar beta-sheet conformation. Therefore, we propose that Abeta(1-40) has a second copper-binding site in a proton-rich environment and the second binding Cu(II) ion interferes with a conformational transition into amyloid fibrils, inducing the formation of granular amorphous aggregates.

Solution NMR Refinement of a Metal Ion Bound Protein Using Metal Ion Inclusive Restrained Molecular Dynamics Methods

PubMed Central

Chakravorty, Dhruva K.; Wang, Bing; Lee, Chul Won; Guerra, Alfredo J.; Giedroc, David P.; Merz, Kenneth M.

2013-01-01

Correctly calculating the structure of metal coordination sites in a protein during the process of nuclear magnetic resonance (NMR) structure determination and refinement continues to be a challenging task. In this study, we present an accurate and convenient means by which to include metal ions in the NMR structure determination process using molecular dynamics (MD) constrained by NMR-derived data to obtain a realistic and physically viable description of the metal binding site(s). This method provides the framework to accurately portray the metal ions and its binding residues in a pseudo-bond or dummy-cation like approach, and is validated by quantum mechanical/molecular mechanical (QM/MM) MD calculations constrained by NMR-derived data. To illustrate this approach, we refine the zinc coordination complex structure of the zinc sensing transcriptional repressor protein Staphylococcus aureus CzrA, generating over 130 ns of MD and QM/MM MD NMR-data compliant sampling. In addition to refining the first coordination shell structure of the Zn(II) ion, this protocol benefits from being performed in a periodically replicated solvation environment including long-range electrostatics. We determine that unrestrained (not based on NMR data) MD simulations correlated to the NMR data in a time-averaged ensemble. The accurate solution structure ensemble of the metal-bound protein accurately describes the role of conformational dynamics in allosteric regulation of DNA binding by zinc and serves to validate our previous unrestrained MD simulations of CzrA. This methodology has potentially broad applicability in the structure determination of metal ion bound proteins, protein folding and metal template protein-design studies. PMID:23609042

Understanding the self-assembly of proteins onto gold nanoparticles and quantum dots driven by metal-histidine coordination.

PubMed

Aldeek, Fadi; Safi, Malak; Zhan, Naiqian; Palui, Goutam; Mattoussi, Hedi

2013-11-26

Coupling of polyhistidine-appended biomolecules to inorganic nanocrystals driven by metal-affinity interactions is a greatly promising strategy to form hybrid bioconjugates. It is simple to implement and can take advantage of the fact that polyhistidine-appended proteins and peptides are routinely prepared using well established molecular engineering techniques. A few groups have shown its effectiveness for coupling proteins onto Zn- or Cd-rich semiconductor quantum dots (QDs). Expanding this conjugation scheme to other metal-rich nanoparticles (NPs) such as AuNPs would be of great interest to researchers actively seeking effective means for interfacing nanostructured materials with biology. In this report, we investigated the metal-affinity driven self-assembly between AuNPs and two engineered proteins, a His7-appended maltose binding protein (MBP-His) and a fluorescent His6-terminated mCherry protein. In particular, we investigated the influence of the capping ligand affinity to the nanoparticle surface, its density, and its lateral extension on the AuNP-protein self-assembly. Affinity gel chromatography was used to test the AuNP-MPB-His7 self-assembly, while NP-to-mCherry-His6 binding was evaluated using fluorescence measurements. We also assessed the kinetics of the self-assembly between AuNPs and proteins in solution, using time-dependent changes in the energy transfer quenching of mCherry fluorescent proteins as they immobilize onto the AuNP surface. This allowed determination of the dissociation rate constant, Kd(-1) ∼ 1-5 nM. Furthermore, a close comparison of the protein self-assembly onto AuNPs or QDs provided additional insights into which parameters control the interactions between imidazoles and metal ions in these systems.

Microfibres and macroscopic films from the coordination-driven hierarchical self-assembly of cylindrical micelles

PubMed Central

Lunn, David J.; Gould, Oliver E. C.; Whittell, George R.; Armstrong, Daniel P.; Mineart, Kenneth P.; Winnik, Mitchell A.; Spontak, Richard J.; Pringle, Paul G.; Manners, Ian

2016-01-01

Anisotropic nanoparticles prepared from block copolymers are of growing importance as building blocks for the creation of synthetic hierarchical materials. However, the assembly of these structural units is generally limited to the use of amphiphilic interactions. Here we report a simple, reversible coordination-driven hierarchical self-assembly strategy for the preparation of micron-scale fibres and macroscopic films based on monodisperse cylindrical block copolymer micelles. Coordination of Pd(0) metal centres to phosphine ligands immobilized within the soluble coronas of block copolymer micelles is found to induce intermicelle crosslinking, affording stable linear fibres comprised of micelle subunits in a staggered arrangement. The mean length of the fibres can be varied by altering the micelle concentration, reaction stoichiometry or aspect ratio of the micelle building blocks. Furthermore, the fibres aggregate on drying to form robust, self-supporting macroscopic micelle-based thin films with useful mechanical properties that are analogous to crosslinked polymer networks, but on a longer length scale. PMID:27538877

What's all the stink about BO-? Using negative molecular ions to measure boron isotopes in samples with trace boron

NASA Astrophysics Data System (ADS)

Hervig, R. L.; Williams, L. B.

2011-12-01

Boron isotope fractionation depends strongly on the coordination of boron in coexisting phases. When boron is tetrahedrally coordinated in one phase and trigonally coordinated in another, equilibrium fractionation can record parameters such as temperature (over a surprisingly wide T for a stable isotope system) or the pH at which phases precipitated from low temperature solutions. The heavy isotope of B is strongly partitioned into fluid phases relative to minerals containing tetrahedrally-coordinated boron and thus B isotope ratios can provide evidence for separation of hydrous fluids from subducted materials and from silicate melts in volcanoes. However, in many cases, the B concentration of relevant solid phases is very low, leading to large errors in the isotope ratio. For example, common analytical protocols for the microanalysis of B on our secondary ion mass spectrometer (SIMS, Cameca 6f) use an O- primary beam, and detection of positive secondary ions at moderate mass resolving power. On samples containing a few ppm B, analyses may require up to ~2 hours to give integrated signals corresponding to errors of +/- 7 per mil (2 sigma). Increases in ion intensity would result from simply increasing the primary current (at the expense of beam diameter) or increasing transmission by reducing mass resolving power (at the expense of including 10BH+ ions on the 11B+ peak). Large magnetic sector SIMS instruments achieve higher transmission at high resolution, but the challenges of obtaining desired precision (+/- 1 permil) remain when boron is present at <2 ppm levels. Another direction to pursue is to find a B-containing ion that is formed more readily than the elemental positive ion. The logical choice is BO-, an ion isoelectronic with F-, and one we would expect to show very high ion yields. However, BO- can be unpleasant to deal with. Isobaric interferences include the toxic species of CN-: various combinations of the two carbon and nitrogen isotopes are silent but deadly additions to the mass spectrum requiring mass resolving powers exceeding 12000 (M/ΔM) for complete separation. In our preliminary studies, we have used a Cs+ primary beam, detection of negative secondary ions and the normal-incidence electron gun for neutralizing positive charge build-up in the crater. The observation of abundant carbon and nitrogen in clay mineral samples reveal the challenges of conducting these analyses. However, carbon and nitrogen contents in other phases of interest are very low, and contaminants can be controlled using careful sample preparation, ultra-high vacuum conditions, and restricting secondary ion detection to the central part of the analyzed crater. Using these conditions, BO- reeks with intensities up to 100x the elemental negative ion! Through a lot of sweat equity, we will demonstrate the use and limitations of BO- in isotope microanalyses of low-B samples. We thank the NSF EAR Instruments and Facilities program for encouraging us to explore new analytical techniques.

CANCELLED Microwave Ion Source and Beam Injection for anAccelerator-Driven Neut ron Source

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

Vainionpaa, J.H.; Gough, R.; Hoff, M.

2007-02-27

An over-dense microwave driven ion source capable of producing deuterium (or hydrogen) beams at 100-200 mA/cm{sup 2} and with atomic fraction > 90% was designed and tested with an electrostatic low energy beam transport section (LEBT). This ion source was incorporated into the design of an Accelerator Driven Neutron Source (ADNS). The other key components in the ADNS include a 6 MeV RFQ accelerator, a beam bending and scanning system, and a deuterium gas target. In this design a 40 mA D{sup +} beam is produced from a 6 mm diameter aperture using a 60 kV extraction voltage. The LEBTmore » section consists of 5 electrodes arranged to form 2 Einzel lenses that focus the beam into the RFQ entrance. To create the ECR condition, 2 induction coils are used to create {approx} 875 Gauss on axis inside the source chamber. To prevent HV breakdown in the LEBT a magnetic field clamp is necessary to minimize the field in this region. Matching of the microwave power from the waveguide to the plasma is done by an autotuner. They observed significant improvement of the beam quality after installing a boron nitride liner inside the ion source. The measured emittance data are compared with PBGUNS simulations.« less

Hybrid simulation of fishbone instabilities in the EAST tokamak

DOE PAGES

Shen, Wei; Wang, Feng; Fu, G. Y.; ...

2017-08-11

Hybrid simulations with the global kinetic-magnetohydrodynamic (MHD) code M3D-K have been carried out to investigate the linear stability and nonlinear dynamics of beam-driven fishbone in the experimental advanced superconducting tokamak (EAST) experiment. Linear simulations show that a low frequency fishbone instability is excited at experimental value of beam ion pressure. The mode is mainly driven by low energy beam ions via precessional resonance. Our results are consistent with the experimental measurement with respect to mode frequency and mode structure. When the beam ion pressure is increased to exceed a critical value, the low frequency mode transits to a beta-induced Alfvenmore » eigenmode (BAE) with much higher frequency. This BAE is driven by higher energy beam ions. Nonlinear simulations show that the frequency of the low frequency fishbone chirps up and down with corresponding hole-clump structures in phase space, consistent with the Berk-Breizman theory. In addition to the low frequency mode, the high frequency BAE is excited during the nonlinear evolution. Furthermore, for the transient case of beam pressure fraction where the low and high frequency modes are simultaneously excited in the linear phase, only one dominant mode appears in the nonlinear phase with frequency jumps up and down during nonlinear evolution.« less

Transport and Stability in C-Mod ITBs in Diverse Regimes

NASA Astrophysics Data System (ADS)

Fiore, C. L.; Ernst, D. R.; Howard, N. T.; Kasten, C. P.; Mikkelsen, D.; Reinke, M. L.; Rice, J. E.; White, A. E.; Rowan, W. L.; Bespamyatnov, I.

2012-10-01

Internal Transport Barriers (ITBs) in C-Mod feature highly peaked density and pressure profiles and are typically induced by the introduction of radio frequency power in the ion cyclotron range of frequencies (ICRF) with the second harmonic of the resonance for minority hydrogen ions positioned off-axis at the plasma half radius on either the low or high field side of the plasma. These ITBs are formed in the absence of particle or momentum injection, and with monotonic q profiles with qmin< 1. Thus they allow exploration of ITB dynamics in a reactor relevant regime. Recently, linear and non-linear gyrokinetic simulations have demonstrated that changes in the ion temperature and plasma rotation profiles, coincident with the application of off-axis ICRF heating, contribute to greater stability to ion temperature gradient driven fluctuation in the plasma. This results in reduced turbulent driven outgoing heat flux. To date, ITB formation in C-Mod has only been observed in EDA H-mode plasmas with moderate (2-3 MW) ICRF power. Experiments to explore the formation of ITBs in other operating regimes such as I-mode and also with high ICRF power are being undertaken to understand further the process of ITB formation and sustainment, especially with regard to turbulent driven transport.

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

Yamamoto, S., E-mail: yamamoto.satoshi.6n@kyoto-u.ac.jp; Kobayashi, S.; Nagasaki, K.

A Faraday-cup type lost-fast ion probe (FLIP) has been designed and installed in Heliotron J for the purpose of the studies of interaction between fast ions and MHD instabilities. The FLIP can measure the co-going fast ions whose energy is in the range of 1.7–42.5 keV (proton) and pitch angle of 90{sup ∘}–140{sup ∘}, especially for fast ions having the injection energy of neutral beam injection (NBI). The FLIP successfully measured the re-entering passing ions and trapped lost-fast ions caused by fast-ion-driven energetic particle modes in NBI heated plasmas.

Effect of Na+ and Ca2+ ions on a lipid Langmuir monolayer: an atomistic description by molecular dynamics simulations.

PubMed

Giner Casares, Juan José; Camacho, Luis; Martín-Romero, Maria Teresa; López Cascales, José Javier

2008-12-01

Studying the effect of alkali and alkaline-earth metal cations on Langmuir monolayers is relevant from biophysical and nanotechnological points of view. In this work, the effect of Na(+) and Ca(2+) on a model of an anionic Langmuir lipid monolayer of dimyristoylphosphatidate (DMPA(-)) is studied by molecular dynamics simulations. The influence of the type of cation on lipid structure, lipid-lipid interactions, and lipid ordering is analyzed in terms of electrostatic interactions. It is found that for a lipid monolayer in its solid phase, the effect of the cations on the properties of the lipid monolayer can be neglected. The influence of the cations is enhanced for the lipid monolayer in its gas phase, where sodium ions show a high degree of dehydration compared with calcium ions. This loss of hydration shell is partly compensated by the formation of lipid-ion-lipid bridges. This difference is ascribed to the higher charge-to-radius ratio q/r for Ca(2+), which makes ion dehydration less favorable compared to Na(+). Owing to the different dehydration behavior of sodium and calcium ions, diminished lipid-lipid coordination, lipid-ion coordination, and lipid ordering are observed for Ca(2+) compared to Na(+). Furthermore, for both gas and solid phases of the lipid Langmuir monolayers, lipid conformation and ion dehydration across the lipid/water interface are studied.

Autonomy and Non-autonomy of Angiogenic Cell Movements Revealed by Experiment-Driven Mathematical Modeling.

PubMed

Sugihara, Kei; Nishiyama, Koichi; Fukuhara, Shigetomo; Uemura, Akiyoshi; Arima, Satoshi; Kobayashi, Ryo; Köhn-Luque, Alvaro; Mochizuki, Naoki; Suda, Toshio; Ogawa, Hisao; Kurihara, Hiroki

2015-12-01

Angiogenesis is a multicellular phenomenon driven by morphogenetic cell movements. We recently reported morphogenetic vascular endothelial cell (EC) behaviors to be dynamic and complex. However, the principal mechanisms orchestrating individual EC movements in angiogenic morphogenesis remain largely unknown. Here we present an experiment-driven mathematical model that enables us to systematically dissect cellular mechanisms in branch elongation. We found that cell-autonomous and coordinated actions governed these multicellular behaviors, and a cell-autonomous process sufficiently illustrated essential features of the morphogenetic EC dynamics at both the single-cell and cell-population levels. Through refining our model and experimental verification, we further identified a coordinated mode of tip EC behaviors regulated via a spatial relationship between tip and follower ECs, which facilitates the forward motility of tip ECs. These findings provide insights that enhance our mechanistic understanding of not only angiogenic morphogenesis, but also other types of multicellular phenomenon. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

The Copper Active Site of CBM33 Polysaccharide Oxygenases

PubMed Central

2013-01-01

The capacity of metal-dependent fungal and bacterial polysaccharide oxygenases, termed GH61 and CBM33, respectively, to potentiate the enzymatic degradation of cellulose opens new possibilities for the conversion of recalcitrant biomass to biofuels. GH61s have already been shown to be unique metalloenzymes containing an active site with a mononuclear copper ion coordinated by two histidines, one of which is an unusual τ-N-methylated N-terminal histidine. We now report the structural and spectroscopic characterization of the corresponding copper CBM33 enzymes. CBM33 binds copper with high affinity at a mononuclear site, significantly stabilizing the enzyme. X-band EPR spectroscopy of Cu(II)-CBM33 shows a mononuclear type 2 copper site with the copper ion in a distorted axial coordination sphere, into which azide will coordinate as evidenced by the concomitant formation of a new absorption band in the UV/vis spectrum at 390 nm. The enzyme’s three-dimensional structure contains copper, which has been photoreduced to Cu(I) by the incident X-rays, confirmed by X-ray absorption/fluorescence studies of both aqueous solution and intact crystals of Cu-CBM33. The single copper(I) ion is ligated in a T-shaped configuration by three nitrogen atoms from two histidine side chains and the amino terminus, similar to the endogenous copper coordination geometry found in fungal GH61. PMID:23540833

Fabricating Bis(phthalocyaninato) Terbium SIM into Tetrakis(phthalocyaninato) Terbium SMM with Enhanced Performance through Sodium Coordination.

PubMed

Chen, Yuxiang; Liu, Chao; Ma, Fang; Qi, Dongdong; Liu, Qingyun; Sun, Hao-Ling; Jiang, Jianzhuang

2018-04-23

The non-peripherally substituted 1,4,8,11,15,18,22,25-octa(butoxy)-phthalocyanine-involved unsymmetrical heteroleptic bis(phthalocyaninato) terbium double-decker, Tb(Pc){H[Pc(α-OC 4 H 9 ) 8 ]} (Pc=unsubstituted phthalocyanine) (1), was revealed to exhibit typical single ion magnet (SIM) behavior with effective energy barrier, 180 K (125 cm -1 ), and blocking temperature, 2 K, due to the severe deviation of the terbium coordination polyhedron from square-antiprismatic geometry. Fabrication of this double-decker compound into the novel tetrakis(phthalocyaninato) terbium pseudo-quadruple-decker Na 2 {Tb(Pc)[Pc(α-OC 4 H 9 ) 8 ]} 2 (2) single molecule magnet (SMM) not only optimizes the coordination polyhedron of terbium ion towards the square-antiprismatic geometry and intensifies the coordination field strength, but more importantly significantly enhances the molecular magnetic anisotropy in the unsymmetrical bis(phthalocyaninato) double-decker unit, along with the change of the counter cation from H + of 1 to Na + of 2, leading to an significantly enhanced magnetic behavior with spin-reversal energy barrier, 528 K (367 cm -1 ), and blocking temperature, 25 K. The present result is surely helpful towards developing novel tetrapyrrole lanthanide SMMs through rational design and self-assembly from bis(tetrapyrrole) lanthanide single ion magnet (SIM) building block. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dynamics of ions in a water drop using the AMOEBA polarizable force field

NASA Astrophysics Data System (ADS)

Thaunay, Florian; Ohanessian, Gilles; Clavaguéra, Carine

2017-03-01

Various ions carrying a charge from -2 to +3 were confined in a drop of 100 water molecules as a way to model coordination properties inside the cluster and at the interface. The behavior of the ions has been followed by molecular dynamics with the AMOEBA polarizable force field. Multiply charged ions and small singly charged ions are found to lie inside the droplet, while bigger monovalent ions sit near the surface. The results provide a coherent picture of average structural properties as well as residence times for which a general trend is proposed, especially for the anions.

A Semianalytical Ion Current Model for Radio Frequency Driven Collisionless Sheaths

NASA Technical Reports Server (NTRS)

Bose, Deepak; Govindan, T. R.; Meyyappan, M.; Arnold, Jim (Technical Monitor)

2001-01-01

We propose a semianalytical ion dynamics model for a collisionless radio frequency biased sheath. The model uses bulk plasma conditions and electrode boundary condition to predict ion impact energy distribution and electrical properties of the sheath. The proposed model accounts for ion inertia and ion current modulation at bias frequencies that are of the same order of magnitude as the ion plasma frequency. A relaxation equation for ion current oscillations is derived which is coupled with a damped potential equation in order to model ion inertia effects. We find that inclusion of ion current modulation in the sheath model shows marked improvements in the predictions of sheath electrical properties and ion energy distribution function.

Drug delivery by water-soluble organometallic cages.

PubMed

Therrien, Bruno

2012-01-01

Until recently, organometallic derivatives were generally viewed as moisture- and air-sensitive compounds, and consequently very challenging to synthesise and very demanding in terms of laboratory requirements (Schlenk techniques, dried solvent, glove box). However, an increasing number of stable, water-soluble organometallic compounds are now available, and organometallic chemistry in aqueous phase is a flourishing area of research. As such, coordination-driven self-assemblies using organometallic building blocks are compatible with water, thus opening new perspectives in bio-organometallic chemistry.This chapter gives a short history of coordination-driven self-assembly, with a special attention to organometallic metalla-cycles, especially those composed of half-sandwich complexes. These metalla-assemblies have been used as sensors, as anticancer agents, as well as drug carriers.

Helicon Modes Driven by Ionosheric 0+ Ions in the Plasma Sheet Region

NASA Technical Reports Server (NTRS)

Lakhina, Gurbax S.; Tsurutani, Bruce T.

1996-01-01

It is shown that the precence of ionospheric-origin oxygen ion beams with anisotropic pressure can excite helicon modes in the near-Earth plasma shet region provided their Alfvenic Mach numbers lie in a certain range.

Impact of ion binding on poly-L-lysine (un)folding energy landscape and kinetics.

PubMed

Xiong, Kan; Asher, Sanford A

2012-06-21

We utilize T-jump UV resonance Raman spectroscopy (UVRR) to study the impact of ion binding on the equilibrium energy landscape and on (un)folding kinetics of poly-L-lysine (PLL). We observe that the relaxation rates of the folded conformations (including π-helix (bulge), pure α-helix, and turns) of PLL are slower than those of short alanine-based peptides. The PLL pure α-helix folding time is similar to that of short alanine-based peptides. We for the first time have directly observed that turn conformations are α-helix and π-helix (bulge) unfolding intermediates. ClO(4)(-) binding to the Lys side chain -NH(3)(+) groups and the peptide backbone slows the α-helix unfolding rate compared to that in pure water, but little impacts the folding rate, resulting in an increased α-helix stability. ClO(4)(-) binding significantly increases the PLL unfolding activation barrier but little impacts the folding barrier. Thus, the PLL folding coordinate(s) differs from the unfolding coordinate(s). The-π helix (bulge) unfolding and folding coordinates do not directly go through the α-helix energy well. Our results clearly demonstrate that PLL (un)folding is not a two-state process.

Crystal structure of bis­(μ-N-hy­droxy­picolin­amid­ato)bis­[bis­(N-hy­droxy­picolinamide)­sodium

PubMed Central

Safyanova, Inna S.; Ohui, Kateryna A.; Omelchenko, Irina V.

2017-01-01

The title compound, [Na2(C6H5N2O2)2(C6H6N2O2)4], is a centrosymmetric coordination dimer based on the sodium(I) salt of N-hy­droxy­picolinamide. The mol­ecule has an {Na2O6(μ-O)2} core with two bridging carbonyl O atoms and two hydroxamate O atoms of two mono-deprotonated residues of N-hy­droxy­picolinamide, while two neutral N-hy­droxy­picolinamide mol­ecules are coordinated in a monodentate manner to each sodium ion via the carbonyl O atoms [the Na—O distances range from 2.3044 (2) to 2.3716 (2) Å]. The penta­coordinated sodium ion exhibits a distorted trigonal–pyramidal coordination polyhedron. In the crystal, the coordination dimers are linked into chains along the c axis via N—H⋯O and N—H⋯N hydrogen bonds; the chains are linked into a two-dimensional framework parallel to (100) via weak C—H⋯O and π–π stacking inter­actions. PMID:28083127

Mechanisms of passive ion permeation through lipid bilayers

PubMed Central

Tepper, Harald L.; Voth, Gregory A.

2008-01-01

Multi-State Empirical Valence Bond and classical Molecular Dynamics simulations were used to explore mechanisms for passive ion leakage through a dimyristoyl phosphatidylcholine (DMPC) lipid bilayer. In accordance with a previous study on proton leakage, it was found that the permeation mechanism must be a highly concerted one, in which ion, solvent and membrane coordinates are coupled. The presence of the ion itself significantly alters the response of those coordinates, suggesting that simulations of transmembrane water structures without explicit inclusion of the ionic solute are insufficient for elucidating transition mechanisms. The properties of H+, Na+, OH-, and bare water molecules in the membrane interior were compared, both by biased sampling techniques and by constructing complete and unbiased transition paths. It was found that the anomalous difference in leakage rates between protons and other cations can be largely explained by charge delocalization effects, rather than the usual kinetic picture (Grotthuss hopping of the proton). Permeability differences between anions and cations through PC bilayers are correlated with suppression of favorable membrane breathing modes by cations. PMID:17048962

Fluoride ion encapsulation by Mg2+ and phosphates in a fluoride riboswitch

PubMed Central

Ren, Aiming; Rajashankar, Kanagalaghatta R.; Patel, Dinshaw J.

2012-01-01

Significant advances in our understanding of RNA architecture, folding and recognition have emerged from structure-function studies on riboswicthes, non-coding RNAs whose sensing domains bind small ligands and whose adjacent expression platforms contain RNA elements involved in the control of gene regulation. We now report on the ligand-bound structure of the Thermotoga petrophila fluoride riboswitch, which adopts a higher-order RNA architecture stabilized by pseudoknot and long-range reversed Watson-Crick and Hoogsteen A•U pair formation. The bound fluoride ion is encapsulated within the junctional architecture, anchored in place through direct coordination to three Mg2+ ions, which in turn are octahedrally coordinated to waters and five inwardly-pointing backbone phosphates. Our structure of the fluoride riboswitch in the bound state defines how RNA can form a binding pocket selective for fluoride, while discriminating against larger halide ions. The T. petrophila fluoride riboswitch most likely functions in gene regulation through a transcription termination mechanism. PMID:22678284

New duel fluorescent "on-off" and colorimetric sensor for Copper(II): Copper(II) binds through N coordination and pi cation interaction to sensor.

PubMed

Kumar, Jutika; Bhattacharyya, Pradip K; Das, Diganta Kumar

2015-03-05

Schiff base derived from naphthylamine and benzil (L) binds to two Cu(2+) ions, one by coordination through N of the Schiff base and another by pi cation interaction through benzil rings. This bonding pattern determined by DFT calculation has been proved by matching electronic spectrum obtained from TDDFT calculation to the experimental one. L acts as "on-off" fluorescent and bare eye detectable colorimetric (purple color) sensor for Cu(2+) ion over the metal ions - Na(+), K(+), Ca(2+) Mn(2+), Co(2+) Ni(2+), Zn(2+), Pb(2+), Cd(2+), Hg(2+), Ag(+), Hg(2+) and Al(3+) in 1:1 v/v CH3CN:H2O. These metal ions do not interfere the fluorescent/colorimetric sensing. As fluorescent sensor the linear range of detection is 5×10(-5) to 3×10(-4)M and detection limit 10(-5)M. Copyright © 2014 Elsevier B.V. All rights reserved.

New duel fluorescent 'on-off' and colorimetric sensor for Copper(II): Copper(II) binds through N coordination and pi cation interaction to sensor

NASA Astrophysics Data System (ADS)

Kumar, Jutika; Bhattacharyya, Pradip K.; Das, Diganta Kumar

2015-03-01

Schiff base derived from naphthylamine and benzil (L) binds to two Cu2+ ions, one by coordination through N of the Schiff base and another by pi cation interaction through benzil rings. This bonding pattern determined by DFT calculation has been proved by matching electronic spectrum obtained from TDDFT calculation to the experimental one. L acts as "on-off" fluorescent and bare eye detectable colorimetric (purple color) sensor for Cu2+ ion over the metal ions - Na+, K+, Ca2+ Mn2+, Co2+ Ni2+, Zn2+, Pb2+, Cd2+, Hg2+, Ag+, Hg2+ and Al3+ in 1:1 v/v CH3CN:H2O. These metal ions do not interfere the fluorescent/colorimetric sensing. As fluorescent sensor the linear range of detection is 5 × 10-5 to 3 × 10-4 M and detection limit 10-5 M.

Bimetallic Metal-Organic Frameworks for Controlled Catalytic Graphitization of Nanoporous Carbons

PubMed Central

Tang, Jing; Salunkhe, Rahul R.; Zhang, Huabin; Malgras, Victor; Ahamad, Tansir; Alshehri, Saad M.; Kobayashi, Naoya; Tominaka, Satoshi; Ide, Yusuke; Kim, Jung Ho; Yamauchi, Yusuke

2016-01-01

Single metal-organic frameworks (MOFs), constructed from the coordination between one-fold metal ions and organic linkers, show limited functionalities when used as precursors for nanoporous carbon materials. Herein, we propose to merge the advantages of zinc and cobalt metals ions into one single MOF crystal (i.e., bimetallic MOFs). The organic linkers that coordinate with cobalt ions tend to yield graphitic carbons after carbonization, unlike those bridging with zinc ions, due to the controlled catalytic graphitization by the cobalt nanoparticles. In this work, we demonstrate a feasible method to achieve nanoporous carbon materials with tailored properties, including specific surface area, pore size distribution, degree of graphitization, and content of heteroatoms. The bimetallic-MOF-derived nanoporous carbon are systematically characterized, highlighting the importance of precisely controlling the properties of the carbon materials. This can be done by finely tuning the components in the bimetallic MOF precursors, and thus designing optimal carbon materials for specific applications. PMID:27471193

Calculation of Vibrational Spectra for Coordinated Thiocyanate Ion in Acetonitrile

NASA Astrophysics Data System (ADS)

Mikhailov, G. P.

2016-07-01

The impact of the association of lithium cation with NCS- ion in acetonitrile on the vibrational spectrum was studied by the density-functional method in the B3LYP/6-31+G(d,p) approximation. The best agreement between experimental and calculated ionic association data was achieved taking into account the nonspecific solvation, oversolvation, and solubility of ionic complexes within the discrete-continuum model. The microstructures of the thiocyanate ion in a contact ion pair with lithium cation and ion-pair dimer and trimer in acetonitrile were established.

Theory of ion Bernstein wave induced shear suppression of turbulence

NASA Astrophysics Data System (ADS)

Craddock, G. G.; Diamond, P. H.; Ono, M.; Biglari, H.

1994-06-01

The theory of radio frequency induced ion Bernstein wave- (IBW) driven shear flow in the edge is examined, with the goal of application of shear suppression of fluctuations. This work is motivated by the observed confinement improvement on IBW heated tokamaks [Phys. Fluids B 5, 241 (1993)], and by previous low-frequency work on RF-driven shear flows [Phys. Rev. Lett. 67, 1535 (1991)]. It is found that the poloidal shear flow is driven electrostatically by both Reynolds stress and a direct ion momentum source, analogous to the concepts of helicity injection and electron momentum input in current drive, respectively. Flow drive by the former does not necessarily require momentum input to the plasma to induce a shear flow. For IBW, the direct ion momentum can be represented by direct electron momentum input, and a charge separation induced stress that imparts little momentum to the plasma. The derived Er profile due to IBW predominantly points inward, with little possibility of direction change, unlike low-frequency Alfvénic RF drive. The profile scale is set by the edge density gradient and electron dissipation. Due to the electrostatic nature of ion Bernstein waves, the poloidal flow contribution dominates in Er. Finally, the necessary edge power absorbed for shear suppression on Princeton Beta Experiment-Modified (PBX-M) [9th Topical Conference on Radio Frequency Power in Plasmas, Charleston, SC, 1991 (American Institute of Physics, New York, 1991), p. 129] is estimated to be 100 kW distributed over 5 cm.

C-H functionalization: thoroughly tuning ligands at a metal ion, a chemist can greatly enhance catalyst's activity and selectivity.

PubMed

Shul'pin, Georgiy B

2013-09-28

This brief essay consists of a few "exciting stories" devoted to relations within a metal-complex catalyst between a metal ion and a coordinated ligand. When, as in the case of a human couple, the rapport of the partners is cordial and a love cements these relations, a chemist finds an ideal married couple, in other words he obtains a catalyst of choice which allows him to functionalize C-H bonds very efficiently and selectively. Examples of such lucky marriages in the catalytic world of ions and ligands are discussed here. Activity of the catalyst is characterized by turnover number (TON) or turnover frequency (TOF) as well as by yield of a target product. Introducing a chelating N,N- or N,O-ligand to the catalyst molecule (this can be an iron or manganese derivative) sharply enhances its activity. However, the activity of vanadium derivatives (with additionally added to the solution pyrazinecarboxylic acid, PCA) as well as of various osmium complexes does not dramatically depend on the nature of ligands surrounding metal ions. Complexes of these metals are very efficient catalysts in oxidations with H2O2. Osmium derivatives are record-holders exhibiting extremely high TONs whereas vanadium complexes are on the second position. Finally, elegant examples of alkane functionalization on the ions of non-transition metals (aluminium, gallium etc.) are described when one ligand within the metal complex (namely, hydroperoxyl ligand HOO(-)) helps other ligand of this complex (H2O2 molecule coordinated to the metal) to disintegrate into two species, generating very reactive hydroxyl radical. Hydrogen peroxide molecule, even ligated to the metal ion, is perfectly stable without the assistance of the neighboring HOO(-) ligand. This ligand can be easily oxidized donating an electron to its partner ligand (H2O2). In an analogous case, when the central ion in the catalyst is a transition metal, this ion changing its oxidation state can donate an electron to the coordinated H2O2 fragment. This provokes the O-O bond rupture in the hydrogen peroxide molecule as is assumed for the role of Fe(2+) ions in the Fenton system.

Investigation of ISIS and Brookhaven National Laboratory ion source electrodes after extended operation

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

Lettry J.; Alessi J.; Faircloth, D.

2012-02-23

Linac4 accelerator of Centre Europeen de Recherches Nucleaires is under construction and a RF-driven H{sup -} ion source is being developed. The beam current requirement for Linac4 is very challenging: 80 mA must be provided. Cesiated plasma discharge ion sources such as Penning or magnetron sources are also potential candidates. Accelerator ion sources must achieve typical reliability figures of 95% and above. Investigating and understanding the underlying mechanisms involved with source failure or ageing is critical when selecting the ion source technology. Plasma discharge driven surface ion sources rely on molybdenum cathodes. Deformation of the cathode surfaces is visible aftermore » extended operation periods. A metallurgical investigation of an ISIS ion source is presented. The origin of the deformation is twofold: Molybdenum sputtering by cesium ions digs few tenths of mm cavities while a growth of molybdenum is observed in the immediate vicinity. The molybdenum growth under hydrogen atmosphere is hard and loosely bound to the bulk. It is, therefore, likely to peel off and be transported within the plasma volume. The observation of the cathode, anode, and extraction electrodes of the magnetron source operated at BNL for two years are presented. A beam simulation of H{sup -}, electrons, and Cs{sup -} ions was performed with the IBSimu code package to qualitatively explain the observations. This paper describes the operation conditions of the ion sources and discusses the metallurgical analysis and beam simulation results.« less

Investigation of ISIS and Brookhaven National Laboratory ion source electrodes after extended operation

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

Lettry, J.; Gerardin, A.; Pereira, H.

2012-02-15

Linac4 accelerator of Centre Europeen de Recherches Nucleaires is under construction and a RF-driven H{sup -} ion source is being developed. The beam current requirement for Linac4 is very challenging: 80 mA must be provided. Cesiated plasma discharge ion sources such as Penning or magnetron sources are also potential candidates. Accelerator ion sources must achieve typical reliability figures of 95% and above. Investigating and understanding the underlying mechanisms involved with source failure or ageing is critical when selecting the ion source technology. Plasma discharge driven surface ion sources rely on molybdenum cathodes. Deformation of the cathode surfaces is visible aftermore » extended operation periods. A metallurgical investigation of an ISIS ion source is presented. The origin of the deformation is twofold: Molybdenum sputtering by cesium ions digs few tenths of mm cavities while a growth of molybdenum is observed in the immediate vicinity. The molybdenum growth under hydrogen atmosphere is hard and loosely bound to the bulk. It is, therefore, likely to peel off and be transported within the plasma volume. The observation of the cathode, anode, and extraction electrodes of the magnetron source operated at BNL for two years are presented. A beam simulation of H{sup -}, electrons, and Cs{sup -} ions was performed with the IBSimu code package to qualitatively explain the observations. This paper describes the operation conditions of the ion sources and discusses the metallurgical analysis and beam simulation results.« less

Optical Trapping of Ion Coulomb Crystals

NASA Astrophysics Data System (ADS)

Schmidt, Julian; Lambrecht, Alexander; Weckesser, Pascal; Debatin, Markus; Karpa, Leon; Schaetz, Tobias

2018-04-01

The electronic and motional degrees of freedom of trapped ions can be controlled and coherently coupled on the level of individual quanta. Assembling complex quantum systems ion by ion while keeping this unique level of control remains a challenging task. For many applications, linear chains of ions in conventional traps are ideally suited to address this problem. However, driven motion due to the magnetic or radio-frequency electric trapping fields sometimes limits the performance in one dimension and severely affects the extension to higher-dimensional systems. Here, we report on the trapping of multiple barium ions in a single-beam optical dipole trap without radio-frequency or additional magnetic fields. We study the persistence of order in ensembles of up to six ions within the optical trap, measure their temperature, and conclude that the ions form a linear chain, commonly called a one-dimensional Coulomb crystal. As a proof-of-concept demonstration, we access the collective motion and perform spectrometry of the normal modes in the optical trap. Our system provides a platform that is free of driven motion and combines advantages of optical trapping, such as state-dependent confinement and nanoscale potentials, with the desirable properties of crystals of trapped ions, such as long-range interactions featuring collective motion. Starting with small numbers of ions, it has been proposed that these properties would allow the experimental study of many-body physics and the onset of structural quantum phase transitions between one- and two-dimensional crystals.

Occurrence of ion upflow associated with ion/electron heating in the polar cap and cusp regions

NASA Astrophysics Data System (ADS)

Ji, E. Y.; Jee, G.; Kwak, Y. S.

2017-12-01

We investigate the occurrence frequency of ion upflow in association with ion/electron heating in the polar cap and cusp regions, using the data obtained from the European Incoherent Scatter Svalbard radar (ESR) during the period of 2000 to 2010. We classify the upflow events by four cases: driven by ion heating (case 1), electron heating (case 2), both ion and electron heatings (case 3), and without any heating (case 4). The statistical analysis of the data shows that the upflow normaly starts at around 350 km altitude and the occurrence seems to peak at 11 MLT. Among the four cases, the occurrence frequency of the upflow is maximized for the case 3 and then followed by case 2, case 1 and case 3, which indicates that both ion and electron heatings are associated with ion upflow. At around 500 km altitude, however, the occurrence frequency is maximized when there is no heating (case 4). We also investigate the dependence of the occurrence frequency of the upflow on Kp and F10.7 indices. The maximum occurrence frequency seems to occur at moderate geomagnetic condition (2 ≤ Kp < 5). As for the solar activity, the occurrence frequency is higher for low solar activity than for high solar activity. The results of this study suggest that the ion upflow occurring in the polar cap/cusp region is mostly driven by both ion and electron heatings.

RF Negative Ion Source Development at IPP Garching

NASA Astrophysics Data System (ADS)

Kraus, W.; McNeely, P.; Berger, M.; Christ-Koch, S.; Falter, H. D.; Fantz, U.; Franzen, P.; Fröschle, M.; Heinemann, B.; Leyer, S.; Riedl, R.; Speth, E.; Wünderlich, D.

2007-08-01

IPP Garching is heavily involved in the development of an ion source for Neutral Beam Heating of the ITER Tokamak. RF driven ion sources have been successfully developed and are in operation on the ASDEX-Upgrade Tokamak for positive ion based NBH by the NB Heating group at IPP Garching. Building on this experience a RF driven H- ion source has been under development at IPP Garching as an alternative to the ITER reference design ion source. The number of test beds devoted to source development for ITER has increased from one (BATMAN) by the addition of two test beds (MANITU, RADI). This paper contains descriptions of the three test beds. Results on diagnostic development using laser photodetachment and cavity ringdown spectroscopy are given for BATMAN. The latest results for long pulse development on MANITU are presented including the to date longest pulse (600 s). As well, details of source modifications necessitated for pulses in excess of 100 s are given. The newest test bed RADI is still being commissioned and only technical details of the test bed are included in this paper. The final topic of the paper is an investigation into the effects of biasing the plasma grid.

Comprehensive approach to fast ion measurements in the beam-driven FRC

NASA Astrophysics Data System (ADS)

Magee, Richard; Smirnov, Artem; Onofri, Marco; Dettrick, Sean; Korepanov, Sergey; Knapp, Kurt; the TAE Team

2015-11-01

The C-2U experiment combines tangential neutral beam injection, edge biasing, and advanced recycling control to explore the sustainment of field-reversed configuration (FRC) plasmas. To study fast ion confinement in such advanced, beam-driven FRCs, a synergetic technique was developed that relies on the measurements of the DD fusion reaction products and the hybrid code Q2D, which treats the plasma as a fluid and the fast ions kinetically. Data from calibrated neutron and proton detectors are used in a complementary fashion to constrain the simulations: neutron detectors measure the volume integrated fusion rate to constrain the total number of fast ions, while proton detectors with multiple lines of sight through the plasma constrain the axial profile of fast ions. One application of this technique is the diagnosis of fast ion energy transfer and pitch angle scattering. A parametric numerical study was conducted, in which additional ad hoc loss and scattering terms of varying strengths were introduced in the code and constrained with measurement. Initial results indicate that the energy transfer is predominantly classical, while, in some cases, non-classical pitch angle scattering can be observed.

Studies of multi-ion-fluid yield anomaly in shock-driven implosions

NASA Astrophysics Data System (ADS)

Rinderknecht, H. G.; Rosenberg, M. J.; Li, C. K.; Zylstra, A. B.; Sio, H.; Gatu Johnson, M.; Frenje, J. A.; Séguin, F. H.; Petrasso, R. D.; Amendt, P. A.; Bellei, C.; Wilks, S. C.; Zimmerman, G.; Hoffman, N. M.; Kagan, G.; Molvig, K.; Glebov, V. Yu.; Stoeckl, C.; Marshall, F. J.; Seka, W.; Delettrez, J. A.; Sangster, T. C.; Betti, R.; Goncharov, V. N.; Meyerhofer, D. D.

2014-10-01

A. NIKROO, GA - Anomalously reduced yields relative to hydrodynamically calculated values have been observed for mixtures of D:3He compared to pure D2 gas-filled implosions in a series of shock-driven implosions at OMEGA. An extensive suite of measurements including temporal and spatial measurements of both the DD- and D3He-fusion reactions were obtained to identify the origin and physics behind this anomalous yield reduction. Measured spectral linewidths of fusion products suggest that the D ions are not thermalized to 3He during the burn, contributing to the reduced yield. The hypothesis that ion-species separation due to diffusive processes contributes to the observed yield reduction is explored using hydrodynamic simulations incorporating ion diffusion. Recent observations by Rosenberg et al. of a yield reduction with increased ion-ion mean free path do not explain the observed anomalous yield trend. Future work that will directly probe species separation with high-precision relative fusion reaction rate measurements between DD-neutrons and D3He-protons using the DualPTD instrument is discussed. This work was supported in part by the U.S. DOE, NLUF, LLE, and LLNL.

Understanding the conductive channel evolution in Na:WO(3-x)-based planar devices.

PubMed

Shang, Dashan; Li, Peining; Wang, Tao; Carria, Egidio; Sun, Jirong; Shen, Baogen; Taubner, Thomas; Valov, Ilia; Waser, Rainer; Wuttig, Matthias

2015-04-14

An ion migration process in a solid electrolyte is important for ion-based functional devices, such as fuel cells, batteries, electrochromics, gas sensors, and resistive switching systems. In this study, a planar sandwich structure is prepared by depositing tungsten oxide (WO(3-x)) films on a soda-lime glass substrate, from which Na(+) diffuses into the WO(3-x) films during the deposition. The entire process of Na(+) migration driven by an alternating electric field is visualized in the Na-doped WO(3-x) films in the form of conductive channel by in situ optical imaging combined with infrared spectroscopy and near-field imaging techniques. A reversible change of geometry between a parabolic and a bar channel is observed with the resistance change of the devices. The peculiar channel evolution is interpreted by a thermal-stress-induced mechanical deformation of the films and an asymmetric Na(+) mobility between the parabolic and the bar channels. These results exemplify a typical ion migration process driven by an alternating electric field in a solid electrolyte with a low ion mobility and are expected to be beneficial to improve the controllability of the ion migration in ion-based functional devices, such as resistive switching devices.

The coordination of boundary tones and its interaction with prominence1

PubMed Central

Katsika, Argyro; Krivokapić, Jelena; Mooshammer, Christine; Tiede, Mark; Goldstein, Louis

2014-01-01

This study investigates the coordination of boundary tones as a function of stress and pitch accent. Boundary tone coordination has not been experimentally investigated previously, and the effect of prominence on this coordination, and whether it is lexical (stress-driven) or phrasal (pitch accent-driven) in nature is unclear. We assess these issues using a variety of syntactic constructions to elicit different boundary tones in an Electromagnetic Articulography (EMA) study of Greek. The results indicate that the onset of boundary tones co-occurs with the articulatory target of the final vowel. This timing is further modified by stress, but not by pitch accent: boundary tones are initiated earlier in words with non-final stress than in words with final stress regardless of accentual status. Visual data inspection reveals that phrase-final words are followed by acoustic pauses during which specific articulatory postures occur. Additional analyses show that these postures reach their achievement point at a stable temporal distance from boundary tone onsets regardless of stress position. Based on these results and parallel findings on boundary lengthening reported elsewhere, a novel approach to prosody is proposed within the context of Articulatory Phonology: rather than seeing prosodic (lexical and phrasal) events as independent entities, a set of coordination relations between them is suggested. The implications of this account for prosodic architecture are discussed. PMID:25300341

Simulating Sources of Superstorm Plasmas

NASA Technical Reports Server (NTRS)

Fok, Mei-Ching

2008-01-01

We evaluated the contributions to magnetospheric pressure (ring current) of the solar wind, polar wind, auroral wind, and plasmaspheric wind, with the surprising result that the main phase pressure is dominated by plasmaspheric protons. We used global simulation fields from the LFM single fluid ideal MHD model. We embedded the Comprehensive Ring Current Model within it, driven by the LFM transpolar potential, and supplied with plasmas at its boundary including solar wind protons, polar wind protons, auroral wind O+, and plasmaspheric protons. We included auroral outflows and acceleration driven by the LFM ionospheric boundary condition, including parallel ion acceleration driven by upward currents. Our plasmasphere model runs within the CRCM and is driven by it. Ionospheric sources were treated using our Global Ion Kinetics code based on full equations of motion. This treatment neglects inertial loading and pressure exerted by the ionospheric plasmas, and will be superceded by multifluid simulations that include those effects. However, these simulations provide new insights into the respective role of ionospheric sources in storm-time magnetospheric dynamics.

Tunable emission in lanthanide coordination polymer gels based on a rationally designed blue emissive gelator.

PubMed

Sutar, Papri; Suresh, Venkata M; Maji, Tapas Kumar

2015-06-18

Rational design and synthesis of a new low molecular weight gelator (LMWG) having 9,10-diphenylanthracene core and terminal terpyridine is reported. Tb(III) and Eu(III) ion coordination to a LMWG results in green and pink emissive coordination polymer gels, respectively, with coiled nanofiber morphology. Further, control over stoichiometry of LMWG:Tb(III):Eu(III) leads to yellow and white light emitting bimetallic gels.

A novel red phosphor of seven-coordinated Mn4+ ion-doped tridecafluorodizirconate Na5Zr2F13 for warm WLEDs.

PubMed

Xi, Luqing; Pan, Yuexiao; Huang, Shaoming; Lian, Hongzhou; Lin, Jun

2018-04-24

Herein, a novel red phosphor based on seven-coordinated Mn4+ ion-doped tridecafluorodizirconate, Na5Zr2F13 (NZF), has been synthesized by stirring a mixture of K2MnF6, NaF, and H2ZrF6 at room temperature. The crystal structure and morphology of the as-obtained phosphor NZF:Mn have been determined by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The composition and distribution of Mn4+ ions in NZF have been confirmed by energy-dispersive spectroscopy (EDS) and element mapping via transmission electron microscopy (TEM). The phosphor NZF:Mn exhibits a strong zero phonon line (ZPL) at 616 nm under excitation of blue light from a GaN light-emitting diode (LED) chip; this is attributed to the low symmetry of Mn4+ ions occupied in a seven-coordinated environment. The luminescence intensity of NZF:Mn has been optimized by controlling the synthesis procedure and synthetic parameters. The luminescence mechanism of the red phosphor NZF:Mn has been investigated according to the detailed experimental results. A warm white light has been produced by a WLED fabricated with the red phosphor NZF:Mn and the commercial yellow phosphor Y3Al5O12:Ce3+ (YAG:Ce) on a GaN LED chip.

Ferromagnetic interactions in Ru(III)-nitronyl nitroxide radical complex: a potential 2p4d building block for molecular magnets.

PubMed

Pointillart, Fabrice; Bernot, Kevin; Sorace, Lorenzo; Sessoli, Roberta; Gatteschi, Dante

2007-07-07

The reaction between [Ru(salen)(PPh3)Cl] and the 4-pyridyl-substituted nitronyl nitroxide radical (NITpPy) leads to the [Ru(salen)(PPh3)(NITpPy)](ClO4)(H2O)2 complex while the reaction with the azido anion (N3-) leads to the [Ru(salen)(PPh3)(N3)] complex 2 (where salen2- = N,N'-ethan-1,2-diylbis(salicylidenamine) and PPh3 = triphenylphosphine). Both compounds have been characterized by single crystal X-ray diffraction. The two crystal structures are composed by a [Ru(III)(salen)(PPh3)]+ unit where the Ru(III) ion is coordinated to a salen2- ligand and one PPh3 ligand in axial position. In 1 the Ru(III) ion is coordinated to the 4-pyridyl-substituted nitronyl nitroxide radical whereas in 2 the second axial position is occupied by the azido ligand. In both complexes the Ru(III) ions are in the same environment RuO2N3P, in a tetragonally elongated octhaedral geometry. The crystal packing of 1 reveals pi-stacking in pairs. While antiferromagnetic intermolecular interaction (J2 = 5.0 cm(-1)) dominates at low temperatures, ferromagnetic intramolecular interaction (J1 = -9.0 cm(-1)) have been found between the Ru(III) ion and the coordinated NITpPy.

Synthesis and characterization of two new zinc(II) coordination polymers with bidentate flexible ligands: Formation of a 2D structure with (44.62)-sql topology

NASA Astrophysics Data System (ADS)

Lalegani, Arash; Khaledi Sardashti, Mohammad; Gajda, Roman; Woźniak, Krzysztof

2017-12-01

Zinc(II) coordination polymers [Zn(bip)2(NCS)2]n (1) and [Zn(μ-bbd)(N3)2]n (2) were synthesized by using the neutral flexible bidentate N-donor ligands 1,4-bis(3,5-dimethylpyrazolyl)butane (bbd) and 1,3-bis(imidazolyl)propane (bip), mono-anionic NCS- or N3-ligand and zinc(II) chloride salts. The results of the X-ray analyses demonstrate that in the structure of 1, the zinc(II) ion is located on an inversion center and exhibits an ZnN6 octahedral arrangement while, in the structure of 2, the zinc(II) ion adopts an ZnN4 tetrahedral geometry. In the polymer 1, the NCS groups are terminally N-bonded to the metal center and the each bip with anti-gauche conformation acts as bridging connecting four zinc(II) ions to form a two-dimensional network with a sql [point symbol (44.62)] topology while, in the polymer 1, the N3 groups are terminally bonded to the metal center and each bbd with anti-anti-anti conformation acts as bridging ligand connecting two zinc(II) ions to form a one-dimensional zig-zag chain. Coordination compounds 1 and 2 have been characterized by infrared spectroscopy, elemental analyses and single-crystal X-ray diffraction. Thermal analyses of polymers were also presented.

The Role of Magnesium for Geometry and Charge in GTP Hydrolysis, Revealed by Quantum Mechanics/Molecular Mechanics Simulations

PubMed Central

Rudack, Till; Xia, Fei; Schlitter, Jürgen; Kötting, Carsten; Gerwert, Klaus

2012-01-01

The coordination of the magnesium ion in proteins by triphosphates plays an important role in catalytic hydrolysis of GTP or ATP, either in signal transduction or energy conversion. For example, in Ras the magnesium ion contributes to the catalysis of GTP hydrolysis. The cleavage of GTP to GDP and Pi in Ras switches off cellular signaling. We analyzed GTP hydrolysis in water, Ras, and Ras·Ras-GTPase-activating protein using quantum mechanics/molecular mechanics simulations. By comparison of the theoretical IR-difference spectra for magnesium ion coordinated triphosphate to experimental ones, the simulations are validated. We elucidated thereby how the magnesium ion contributes to catalysis. It provides a temporary storage for the electrons taken from the triphosphate and it returns them after bond cleavage and Pi release back to the diphosphate. Furthermore, the Ras·Mg2+ complex forces the triphosphate into a stretched conformation in which the β- and γ-phosphates are coordinated in a bidentate manner. In this conformation, the triphosphate elongates the bond, which has to be cleaved during hydrolysis. Furthermore, the γ-phosphate adopts a more planar structure, driving the conformation of the molecule closer to the hydrolysis transition state. GTPase-activating protein enhances these changes in GTP conformation and charge distribution via the intruding arginine finger. PMID:22853907

The Population Care Coordination Process.

PubMed

Rushton, Sharron

2015-01-01

The purpose of the article was to outline a population-based approach to providing care coordination. The Population Care Coordination Process provides a framework for each provider and/or organization to provide multilevel care based on population- and patient-centered principles. The Population Care Coordination Process is scalable. It can be utilized in a smaller scale such as single provider office or in a larger scale such as an accountable care organization. There are many issues within our current health care structure that must be addressed. Care coordination has been identified as a potential solution to address the needs of complex patients within the system. The expansion to consider populations allows for a more targeted and efficient approach. The population care process entails a data-driven approach to care coordination. The inclusion of populations in the care coordination process provides an opportunity to maximize efforts and improve outcomes.

Dynamics of a reconnection-driven runaway ion tail in a reversed field pinch plasma

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

Anderson, J. K., E-mail: jkanders@wisc.edu; Kim, J.; Bonofiglo, P. J.

2016-05-15

While reconnection-driven ion heating is common in laboratory and astrophysical plasmas, the underlying mechanisms for converting magnetic to kinetic energy remain not fully understood. Reversed field pinch discharges are often characterized by rapid ion heating during impulsive reconnection, generating an ion distribution with an enhanced bulk temperature, mainly perpendicular to magnetic field. In the Madison Symmetric Torus, a subset of discharges with the strongest reconnection events develop a very anisotropic, high energy tail parallel to magnetic field in addition to bulk perpendicular heating, which produces a fusion neutron flux orders of magnitude higher than that expected from a Maxwellian distribution.more » Here, we demonstrate that two factors in addition to a perpendicular bulk heating mechanism must be considered to explain this distribution. First, ion runaway can occur in the strong parallel-to-B electric field induced by a rapid equilibrium change triggered by reconnection-based relaxation; this effect is particularly strong on perpendicularly heated ions which experience a reduced frictional drag relative to bulk ions. Second, the confinement of ions varies dramatically as a function of velocity. Whereas thermal ions are governed by stochastic diffusion along tearing-altered field lines (and radial diffusion increases with parallel speed), sufficiently energetic ions are well confined, only weakly affected by a stochastic magnetic field. High energy ions traveling mainly in the direction of toroidal plasma current are nearly classically confined, while counter-propagating ions experience an intermediate confinement, greater than that of thermal ions but significantly less than classical expectations. The details of ion confinement tend to reinforce the asymmetric drive of the parallel electric field, resulting in a very asymmetric, anisotropic distribution.« less

rf improvements for Spallation Neutron Source H- ion sourcea)

NASA Astrophysics Data System (ADS)

Kang, Y. W.; Fuja, R.; Goulding, R. H.; Hardek, T.; Lee, S.-W.; McCarthy, M. P.; Piller, M. C.; Shin, K.; Stockli, M. P.; Welton, R. F.

2010-02-01

The Spallation Neutron Source at Oak Ridge National Laboratory is ramping up the accelerated proton beam power to 1.4 MW and just reached 1 MW. The rf-driven multicusp ion source that originates from the Lawrence Berkeley National Laboratory has been delivering ˜38 mA H- beam in the linac at 60 Hz, 0.9 ms. To improve availability, a rf-driven external antenna multicusp ion source with a water-cooled ceramic aluminum nitride (AlN) plasma chamber is developed. Computer modeling and simulations have been made to analyze and optimize the rf performance of the new ion source. Operational statistics and test runs with up to 56 mA medium energy beam transport beam current identify the 2 MHz rf system as a limiting factor in the system availability and beam production. Plasma ignition system is under development by using a separate 13 MHz system. To improve the availability of the rf power system with easier maintenance, we tested a 70 kV isolation transformer for the 80 kW, 6% duty cycle 2 MHz amplifier to power the ion source from a grounded solid-state amplifier.

rf improvements for Spallation Neutron Source H- ion source.

PubMed

Kang, Y W; Fuja, R; Goulding, R H; Hardek, T; Lee, S-W; McCarthy, M P; Piller, M C; Shin, K; Stockli, M P; Welton, R F

2010-02-01

The Spallation Neutron Source at Oak Ridge National Laboratory is ramping up the accelerated proton beam power to 1.4 MW and just reached 1 MW. The rf-driven multicusp ion source that originates from the Lawrence Berkeley National Laboratory has been delivering approximately 38 mA H(-) beam in the linac at 60 Hz, 0.9 ms. To improve availability, a rf-driven external antenna multicusp ion source with a water-cooled ceramic aluminum nitride (AlN) plasma chamber is developed. Computer modeling and simulations have been made to analyze and optimize the rf performance of the new ion source. Operational statistics and test runs with up to 56 mA medium energy beam transport beam current identify the 2 MHz rf system as a limiting factor in the system availability and beam production. Plasma ignition system is under development by using a separate 13 MHz system. To improve the availability of the rf power system with easier maintenance, we tested a 70 kV isolation transformer for the 80 kW, 6% duty cycle 2 MHz amplifier to power the ion source from a grounded solid-state amplifier.

Ion beam nanopatterning of III-V semiconductors: Consistency of experimental and simulation trends within a chemistry-driven theory

DOE PAGES

El-Atwani, O.; Norris, S. A.; Ludwig, K.; ...

2015-12-16

In this study, several proposed mechanisms and theoretical models exist concerning nanostructure evolution on III-V semiconductors (particularly GaSb) via ion beam irradiation. However, making quantitative contact between experiment on the one hand and model-parameter dependent predictions from different theories on the other is usually difficult. In this study, we take a different approach and provide an experimental investigation with a range of targets (GaSb, GaAs, GaP) and ion species (Ne, Ar, Kr, Xe) to determine new parametric trends regarding nanostructure evolution. Concurrently, atomistic simulations using binary collision approximation over the same ion/target combinations were performed to determine parametric trends onmore » several quantities related to existing model. A comparison of experimental and numerical trends reveals that the two are broadly consistent under the assumption that instabilities are driven by chemical instability based on phase separation. Furthermore, the atomistic simulations and a survey of material thermodynamic properties suggest that a plausible microscopic mechanism for this process is an ion-enhanced mobility associated with energy deposition by collision cascades.« less

Effect of the helically-trapped energetic-ion-driven resistive interchange modes on energetic ion confinement in the Large Helical Device

NASA Astrophysics Data System (ADS)

Ogawa, K.; Isobe, M.; Kawase, H.; Nishitani, T.; Seki, R.; Osakabe, M.; LHD Experiment Group

2018-04-01

The effect of the helically-trapped energetic-ion-driven resistive interchange modes (EICs) on energetic ion confinement is studied in the Large Helical Device deuterium plasmas. Neutron diagnostics such as the neutron flux monitor and the vertical neutron camera (VNC) are used in order to measure neutrons mainly created by beam-plasma reactions. The line-integrated neutron profiles are obtained by VNC in magnetohydrodynamic-quiet plasma with various neutral beam (NB) injection patterns. The profiles are consistent with that expected by the beam ion density calculated using orbit-following simulations. Significant decreases of the total neutron emission rate (S n) and the neutron counting rate of the VNC (C n) in central cords are observed to be synchronized with EIC bursts with perpendicular-NB injection. The drop rates of both S n and C n increase with EIC amplitude and reach around 50%. The line-integrated neutron profiles before and after EIC burst show that in the central cords, C n decrease due to EIC burst whereas there is almost no change in the other cords. The experimental results suggests that the effect of EIC on helically-trapped beam ion is substantial, however the effect of passing beam ion is not significant.

Two mixed-ligand lanthanide–hydrazone complexes: [Pr(NCS)3(pbh)2]·H2O and [Nd(NCS)(NO3)(pbh)2(H2O)]NO3·2.33H2O [pbh is N′-(pyridin-2-ylmethylidene)benzo­hydrazide, C13H11N3O

PubMed Central

Paschalidis, Damianos G.; Harrison, William T. A.

2016-01-01

The gel-mediated syntheses and crystal structures of [N′-(pyridin-2-ylmethylidene-κN)benzohydrazide-κ2 N′,O]tris(thiocyanato-κN)praseodymium(III) mono­hydrate, [Pr(NCS)3(C13H11N3O)2]·H2O, (I), and aqua(nitrato-κ2 O,O′)[N′-(pyri­din-2-ylmethylidene-κN)benzohydrazide-κ2 N′,O](thiocyanato-κN)neo­dym­ium(III) nitrate 2.33-hydrate, [Nd(NCS)(NO3)(C13H11N3O)2(H2O)]NO3·2.33H2O, (II), are reported. The Pr3+ ion in (I) is coordinated by two N,N,O-tridentate N′-(pyridin-2-ylmethylidene)benzohydrazide (pbh) ligands and three N-bonded thio­cyanate ions to generate an irregular PrN7O2 coordination polyhedron. The Nd3+ ion in (II) is coordinated by two N,N,O-tridentate pbh ligands, an N-bonded thio­cyanate ion, a bidentate nitrate ion and a water mol­ecule to generate a distorted NdN5O5 bicapped square anti­prism. The crystal structures of (I) and (II) feature numerous hydrogen bonds, which lead to the formation of three-dimensional networks in each case. PMID:26958385

Ion transfer through solvent polymeric membranes driven by an exponential current flux.

PubMed

Molina, A; Torralba, E; González, J; Serna, C; Ortuño, J A

2011-03-21

General analytical equations which govern ion transfer through liquid membranes with one and two polarized interfaces driven by an exponential current flux are derived. Expressions for the transient and stationary E-t, dt/dE-E and dI/dE-E curves are obtained, and the evolution from transient to steady behaviour has been analyzed in depth. We have also shown mathematically that the voltammetric and stationary chronopotentiometric I(N)-E curves are identical (with E being the applied potential for voltammetric techniques and the measured potential for chronopotentiometric techniques), and hence, their derivatives provide identical information.

Metastable Se6 as a ligand for Ag+: from isolated molecular to polymeric 1D and 2D structures.

PubMed

Aris, Damian; Beck, Johannes; Decken, Andreas; Dionne, Isabelle; Schmedt auf der Günne, Jörn; Hoffbauer, Wilfried; Köchner, Tobias; Krossing, Ingo; Passmore, Jack; Rivard, Eric; Steden, Folker; Wang, Xinping

2011-06-14

Attempts to prepare the hitherto unknown Se(6)(2+) cation by the reaction of elemental selenium and Ag[A] ([A](-) = [Sb(OTeF(5))(6)](-), [Al(OC(CF(3))(3))(4)](-)) in SO(2) led to the formation of [(OSO)Ag(Se(6))Ag(OSO)][Sb(OTeF(5))(6)](2)1 and [(OSO)(2)Ag(Se(6))Ag(OSO)(2)][Al(OC(CF(3))(3))(4)](2)2a. 1 could only be prepared by using bromine as co-oxidant, however, bulk 2b (2a with loss of SO(2)) was accessible from Ag[Al(OC(CF(3))(3))(4)] and grey Se in SO(2) (chem. analysis). The reactions of Ag[MF(6)] (M = As, Sb) and elemental selenium led to crystals of 1/∞{[Ag(Se(6))](∞)[Ag(2)(SbF(6))(3)](∞)} 3 and {1/∞[Ag(Se(6))Ag](∞)}[AsF(6)](2)4. Pure bulk 4 was best prepared by the reaction of Se(4)[AsF(6)](2), silver metal and elemental selenium. Attempts to prepare bulk 1 and 3 were unsuccessful. 1-4 were characterized by single-crystal X-ray structure determinations, 2b and 4 additionally by chemical analysis and 4 also by X-ray powder diffraction, FT-Raman and FT-IR spectroscopy. Application of the PRESTO III sequence allowed for the first time (109)Ag MAS NMR investigations of 4 as well as AgF, AgF(2), AgMF(6) and {1/∞[Ag(I(2))](∞)}[MF(6)] (M = As, Sb). Compounds 1 and 2a/b, with the very large counter ions, contain isolated [Ag(Se(6))Ag](2+) heterocubane units consisting of a Se(6) molecule bicapped by two silver cations (local D(3d) sym). 3 and 4, with the smaller anions, contain close packed stacked arrays of Se(6) rings with Ag(+) residing in octahedral holes. Each Ag(+) ion coordinates to three selenium atoms of each adjacent Se(6) ring. 4 contains [Ag(Se(6))(+)](∞) stacks additionally linked by Ag(2)(+) into a two dimensional network. 3 features a remarkable 3-dimensional [Ag(2)(SbF(6))(3)](-) anion held together by strong Sb-FAg contacts between the component Ag(+) and [SbF(6)](-) ions. The hexagonal channels formed by the [Ag(2)(SbF(6))(3)](-) anions are filled by stacks of [Ag(Se(6))(+)](∞) cations. Overall 1-4 are new members of the rare class of metal complexes of neutral main group elemental clusters, in which the main group element is positively polarized due to coordination to a metal ion. Notably, 1 to 4 include the commonly metastable Se(6) molecule as a ligand. The structure, bonding and thermodynamics of 1 to 4 were investigated with the help of quantum chemical calculations (PBE0/TZVPP and (RI-)MP2/TZVPP, in part including COSMO solvation) and Born-Fajans-Haber-cycle calculations. From an analysis of all the available data it appears that the formation of the usually metastable Se(6) molecule from grey selenium is thermodynamically driven by the coordination to the Ag(+) ions.

The importance of dehydration in determining ion transport in narrow pores.

PubMed

Richards, Laura A; Schäfer, Andrea I; Richards, Bryce S; Corry, Ben

2012-06-11

The transport of hydrated ions through narrow pores is important for a number of processes such as the desalination and filtration of water and the conductance of ions through biological channels. Here, molecular dynamics simulations are used to systematically examine the transport of anionic drinking water contaminants (fluoride, chloride, nitrate, and nitrite) through pores ranging in effective radius from 2.8 to 6.5 Å to elucidate the role of hydration in excluding these species during nanofiltration. Bulk hydration properties (hydrated size and coordination number) are determined for comparison with the situations inside the pores. Free energy profiles for ion transport through the pores show energy barriers depend on pore size, ion type, and membrane surface charge and that the selectivity sequence can change depending on the pore size. Ion coordination numbers along the trajectory showed that partial dehydration of the transported ion is the main contribution to the energy barriers. Ion transport is greatly hindered when the effective pore radius is smaller than the hydrated radius, as the ion has to lose some associated water molecules to enter the pore. Small energy barriers are still observed when pore sizes are larger than the hydrated radius due to re-orientation of the hydration shell or the loss of more distant water. These results demonstrate the importance of ion dehydration in transport through narrow pores, which increases the current level of mechanistic understanding of membrane-based desalination and transport in biological channels. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Triboelectrification-Enabled Self-Powered Detection and Removal of Heavy Metal Ions in Wastewater.

PubMed

Li, Zhaoling; Chen, Jun; Guo, Hengyu; Fan, Xing; Wen, Zhen; Yeh, Min-Hsin; Yu, Chongwen; Cao, Xia; Wang, Zhong Lin

2016-04-20

A fundamentally new working principle into the field of self-powered heavy-metal-ion detection and removal using the triboelectrification effect is introduced. The as-developed tribo-nanosensors can selectively detect common heavy metal ions. The water-driven triboelectric nanogenerator is taken as a sustainable power source for heavy-metal-ion removal by recycling the kinetic energy from flowing wastewater. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Operation and development status of the J-PARC ion source

NASA Astrophysics Data System (ADS)

Yamazaki, S.; Ikegami, K.; Ohkoshi, K.; Ueno, A.; Koizumi, I.; Takagi, A.; Oguri, H.

2014-02-01

A cesium-free H- ion source driven with a LaB6 filament is being operated at the Japan Proton Accelerator Research Complex (J-PARC) without any serious trouble since the restoration from the March 2011 earthquake. The H- ion current from the ion source is routinely restricted approximately 19 mA for the lifetime of the filament. In order to increase the beam power at the linac beam operation (January to February 2013), the beam current from the ion source was increased to 22 mA. At this operation, the lifetime of the filament was estimated by the reduction in the filament current. According to the steep reduction in the filament current, the break of the filament was predicted. Although the filament has broken after approximately 10 h from the steep current reduction, the beam operation was restarted approximately 8 h later by the preparation for the exchange of new filament. At the study time for the 3 GeV rapid cycling synchrotron (April 2013), the ion source was operated at approximately 30 mA for 8 days. As a part of the beam current upgrade plan for the J-PARC, the front end test stand consisting of the ion source and the radio frequency quadrupole is under preparation. The RF-driven H- ion source developed for the J-PARC 2nd stage requirements will be tested at this test stand.

Comparison of Measurement And Modeling Of Current Profile Changes Due To Neutral Bean Ion Redistribution During TAE Avalanches in NSTX

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

Darrow, Douglas

Brief "avalanches" of toroidal Alfven eigenmodes (TAEs) are observed in NSTX plasmas with several different n numbers simultaneously present. These affect the neutral beam ion distribution as evidenced by a concurrent drop in the neutron rate and, sometimes, beam ion loss. Guiding center orbit modeling has shown that the modes can transiently render portions of the beam ion phase space stochastic. The resulting redistribution of beam ions can also create a broader beam-driven current profile and produce other changes in the beam ion distribution function

Runaway of energetic test ions in a toroidal plasma

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

Eilerman, S., E-mail: eilerman@wisc.edu; Anderson, J. K.; Sarff, J. S.

2015-02-15

Ion runaway in the presence of a large-scale, reconnection-driven electric field has been conclusively measured in the Madison Symmetric Torus reversed-field pinch (RFP). Measurements of the acceleration of a beam of fast ions agree well with test particle and Fokker-Planck modeling of the runaway process. However, the runaway mechanism does not explain all measured ion heating in the RFP, particularly previous measurements of strong perpendicular heating. It is likely that multiple energization mechanisms occur simultaneously and with differing significance for magnetically coupled thermal ions and magnetically decoupled tail and beam ions.

Crystal structure of pentasodium hydrogen dicitrate from synchrotron X-ray powder diffraction data and DFT comparison

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

Rammohan, Alagappa; Kaduk, James A.

2017-01-27

The crystal structure of pentasodium hydrogen dicitrate, Na 5H(C 6H 5O 7) 2, has been solved and refined using synchrotron X-ray powder diffraction data, and optimized using density functional techniques. Each of the two independent citrate anions is joined into a dimer by very strong centrosymmetric O—H...O hydrogen bonds, with O...O distances of 2.419 and 2.409 Å. Four octahedrally coordinated Na +ions share edges to form open layers parallel to theabplane. A fifth Na +ion in trigonal–bipyramidal coordination shares faces with NaO 6octahedra on both sides of these layers.

Core-Shell Coating Silicon Anode Interfaces with Coordination Complex for Stable Lithium-Ion Batteries.

PubMed

Zhou, Jinqiu; Qian, Tao; Wang, Mengfan; Xu, Na; Zhang, Qi; Li, Qun; Yan, Chenglin

2016-03-02

In situ core-shell coating was used to improve the electrochemical performance of Si-based anodes with polypyrrole-Fe coordination complex. The vast functional groups in the organometallic coordination complex easily formed hydrogen bonds when in situ modifying commercial Si nanoparticles. The incorporation of polypyrrole-Fe resulted in the conformal conductive coating surrounding each Si nanoparticle, not only providing good electrical connection to the particles but also promoting the formation of a stable solid-electrolyte-interface layer on the Si electrode surface, enhancing the cycling properties. As an anode material for Li-ion batteries, modified silicon powders exhibited high reversible capacity (3567 mAh/g at 0.3 A/g), good rate property (549.12 mAh/g at 12 A/g), and excellent cycling performance (reversible capacity of 1500 mAh/g after 800 cycles at 1.2 A/g). The constructed novel concept of core-shell coating Si particles presented a promising route for facile and large-scale production of Si-based anodes for extremely durable Li-ion batteries, which provided a wide range of applications in the field of energy storage of the renewable energy derived from the solar energy, hydropower, tidal energy, and geothermal heat.

Cobalt ion-coordinated self-assembly synthesis of nitrogen-doped ordered mesoporous carbon nanosheets for efficiently catalyzing oxygen reduction.

PubMed

Wang, Haitao; Wang, Wei; Asif, Muhammad; Yu, Yang; Wang, Zhengyun; Wang, Junlei; Liu, Hongfang; Xiao, Junwu

2017-10-19

The design and synthesis of a promising porous carbon-based electrocatalyst with an ordered and uninterrupted porous structure for oxygen reduction reaction (ORR) is still a significant challenge. Herein, an efficient catalyst based on cobalt-embedded nitrogen-doped ordered mesoporous carbon nanosheets (Co/N-OMCNS) is successfully prepared through a two-step procedure (cobalt ion-coordinated self-assembly and carbonization process) using 3-aminophenol as a nitrogen source, cobalt acetate as a cobalt source and Pluronic F127 as a mesoporous template. This work indicates that the formation of a two dimensional nanosheet structure is directly related to the extent of the cobalt ion coordination interaction. Moreover, the critical roles of pyrolysis temperature in nitrogen doping and ORR catalytic activity are also investigated. Benefiting from the high surface area and graphitic degree, high contents of graphitic N and pyridinic N, ordered interconnected mesoporous carbon framework, as well as synergetic interaction between the cobalt nanoparticles and protective nitrogen doped graphitic carbon layer, the resultant optimal catalyst Co/N-OMCNS-800 (pyrolyzed at 800 °C) exhibits comparable ORR catalytic activity to Pt/C, superior tolerance to methanol crossover and stability.

A new three-dimensional bis(benzimidazole)-based cadmium(II) coordination polymer

NASA Astrophysics Data System (ADS)

Hao, Shao Yun; Hou, Suo Xia; Hao, Zeng Chuan; Cui, Guang Hua

2018-01-01

A new coordination polymer (CP), formulated as [Cd(L)(DCTP)]n (1) (L = 1,1‧-(1,4-butanediyl)bis(2-methylbenzimidazole), H2DCTP = 2,5-dichloroterephthalic acid), was synthesized under hydrothermal conditions and the performance as luminescent probe was also investigated. Single-crystal X-ray diffraction reveals CP 1 is a 3D 3-fold interpenetrated dia network with large well-defined pores. It is found that CP 1 revealed highly sensitive luminescence sensing for Fe3 + ions in acetonitrile solution with a high quenching efficiency of KSV = 2541.238 L·mol- 1 and a low detection limit of 3.2 μM (S/N = 3). Moreover, the photocatalytic efficiency of 1 for degradation of methylene blue could reach 82.8% after 135 min. Therefore, this coordination polymer could be viewed as multifunctional material for selectively sensing Fe3 + ions and effectively degrading dyes.

Synthesis and characterization of bright green terbium coordination complex derived from 1,4-bis(carbonylmethyl)terephthalate: Structure and luminescence properties

NASA Astrophysics Data System (ADS)

Ma, Mengjiao; Li, Congcong; Shu, Dengkun; Wang, Chaohua; Xi, Peng

2018-02-01

A photoluminescent terbium (Tb) complex involving a novel benzoic-acid compound with a unique coordinated structure, namely 1,4-bis(carbonylmethyl)terephthalate (BCMT), has been designed and synthesized. The new coordinate structure and energy-transfer mechanism between the ligand and Tb(III) ions were investigated in detail. The results demonstrated that the BCMT-Tb(III) complex shows strong fluorescence intensity (4 × 106 a.u.) and long fluorescence lifetime (1.302 ms), owing to the favorable degree of energy matching between the triplet excited level of the ligand and the resonant level of Tb(III) ions. Based on the analysis of three-dimensional luminescence spectra, the as-prepared Tb(III) complex can be effectively excited in the range of 250-310 nm, and it shows high color purity, with a bright green appearance.

Recovery of metals from simulant spent lithium-ion battery as organophosphonate coordination polymers in aqueous media.

PubMed

Perez, Emilie; Andre, Marie-Laure; Navarro Amador, Ricardo; Hyvrard, François; Borrini, Julien; Carboni, Michaël; Meyer, Daniel

2016-11-05

An innovative approach is proposed for the recycling of metals from a simulant lithium-ion battery (LIBs) waste aqueous solution. Phosphonate organic linkers are introduced as precipitating agents to selectively react with the metals to form coordination polymers from an aqueous solution containing Ni, Mn and Co in a hydrothermal process. The supernatant is analyzed by ICP-AES to quantify the efficiency and the selectivity of the precipitation and the materials are characterized by Scanning Electron Microscopy (SEM), Powder X-Ray Diffraction (PXRD), Thermogravimetric Analyses (TGA) and nitrogen gas sorption (BET). Conditions have been achieved to selectively precipitate Manganese or Manganese/Cobalt from this solution with a high efficiency. This work describes a novel method to obtain potentially valuable coordination polymers from a waste metal solution that can be generalized on any waste solution. Copyright © 2016 Elsevier B.V. All rights reserved.

Real space mapping of Li-ion transport in amorphous Si anodes with nanometer resolution.

PubMed

Balke, Nina; Jesse, Stephen; Kim, Yoongu; Adamczyk, Leslie; Tselev, Alexander; Ivanov, Ilia N; Dudney, Nancy J; Kalinin, Sergei V

2010-09-08

The electrical bias driven Li-ion motion in silicon anode materials in thin film battery heterostructures is investigated using electrochemical strain microscopy (ESM), which is a newly developed scanning probe microscopy based characterization method. ESM utilizes the intrinsic link between bias-controlled Li-ion concentration and molar volume of electrode materials, providing the capability for studies on the sub-20 nm scale, and allows the relationship between Li-ion flow and microstructure to be established. The evolution of Li-ion transport during the battery charging is directly observed.

Thomson-Scattering Study of the Subharmonic Decay of Ion-Acoustic Waves Driven by the Brillouin Instability

NASA Astrophysics Data System (ADS)

Bandulet, H. C.; Labaune, C.; Lewis, K.; Depierreux, S.

2004-07-01

Thomson scattering (TS) has been used to investigate the two-ion decay instability of ion acoustic waves generated by stimulated Brillouin scattering in an underdense CH plasma. Two complementary TS diagnostics, spectrally and spatially resolved, demonstrate the occurrence of the subharmonic decay of the primary ion acoustic wave into two secondary waves. The study of the laser intensity dependence shows that the secondary ion acoustic waves are correlated with the SBS reflectivity saturation, at a level of a few percent.

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

Koivisto, H., E-mail: hannu.koivisto@phys.jyu.fi; Kalvas, T.; Tarvainen, O.

Several ion source related research and development projects are in progress at the Department of Physics, University of Jyväskylä (JYFL). The work can be divided into investigation of the ion source plasma and development of ion sources, ion beams, and diagnostics. The investigation covers the Electron Cyclotron Resonance Ion Source (ECRIS) plasma instabilities, vacuum ultraviolet (VUV) and visible light emission, photon induced electron emission, and the development of plasma diagnostics. The ion source development covers the work performed for radiofrequency-driven negative ion source, RADIS, beam line upgrade of the JYFL 14 GHz ECRIS, and the development of a new room-temperature-magnetmore » 18 GHz ECRIS, HIISI.« less

Synthesis of non-toxic As and Cr nanoparticles through redox activity of highly flexible layered coordination polymer of Ni(II).

PubMed

Agarwal, Rashmi A

2018-03-09

A simple method for the sequestration of As(III) and Cr(VI) from water has been demonstrated by utilizing a highly flexible porous coordination polymer (PCP) of Ni(II) in its as synthesized form or without solvent removal. This PCP reduces the high toxicity of As(III) and Cr(VI) ions into non-toxic As(0) and Cr/Cr 2 O 3 /CrO 2 (zero, tri and tetravalent) nanoparticles (NPs) within its pores, and this is characterized by powder x-ray diffraction, x-ray photoelectron spectroscopy and high-resolution transmission electron microscopy analysis. The high functionality of this polymer is due to the presence of monodentate carboxylate groups of a benzenetricarboxylate linker, which provide anchoring sites to the metal ions of the metal precursors. Due to the highly oxidising nature of these toxic ions, a redox reaction takes place between the framework metal ions and toxic metal ions, which is explained by an electron paramagnetic resonance study. This is the first report to synthesize non-toxic, as well as useful, NPs of As and Cr from their highly toxic ions within the cavities of a PCP for remediation of the toxic waste stream and contaminated waste water.

Synthesis and luminescence properties of CaSnO3 :Bi3+ blue phosphor and the emission improvement by Li+ ion.

PubMed

Cao, Renping; Zhang, Jinlong; Wang, Wudi; Hu, Qianglin; Li, Wensheng; Ruan, Wen; Ao, Hui

2017-09-01

CaSnO 3 :Bi 3+ blue-emitting phosphor was synthesized using a high-temperature solid-state reaction method in air. The crystal structures and luminescence properties were investigated. A broad emission band peaking at ~448 nm upon excitation at 262 and 308 nm was observed in the range 330-680 nm at room temperature due to 3 P 1  →  1 S 0 transition of the Bi 3+ ion. The chromaticity coordinate was (0.1786, 0.1665). The optimal Bi 3+ ion concentration was ~0.6 mol% in CaSnO 3 :Bi 3+ phosphor. The emission spectrum of CaSnO 3 :Bi 3+ phosphor showed a blue-shift with increasing temperature from 50 to 300 K due to the influence of temperature on the electron transition of the Bi 3+ ion. The emission intensity of CaSnO 3 :Bi 3+ phosphor may be increased ~1.45 times by co-doping Li + ions as a charge compensator and fluxing agent. The luminescence mechanism is explained by a configurational coordinate diagram of Bi 3+ ion in CaSnO 3 :Bi 3+ phosphor. Copyright © 2017 John Wiley & Sons, Ltd.

Synthesis of non-toxic As and Cr nanoparticles through redox activity of highly flexible layered coordination polymer of Ni(II)

NASA Astrophysics Data System (ADS)

Agarwal, Rashmi A.

2018-03-01

A simple method for the sequestration of As(III) and Cr(VI) from water has been demonstrated by utilizing a highly flexible porous coordination polymer (PCP) of Ni(II) in its as synthesized form or without solvent removal. This PCP reduces the high toxicity of As(III) and Cr(VI) ions into non-toxic As(0) and Cr/Cr2O3/CrO2 (zero, tri and tetravalent) nanoparticles (NPs) within its pores, and this is characterized by powder x-ray diffraction, x-ray photoelectron spectroscopy and high-resolution transmission electron microscopy analysis. The high functionality of this polymer is due to the presence of monodentate carboxylate groups of a benzenetricarboxylate linker, which provide anchoring sites to the metal ions of the metal precursors. Due to the highly oxidising nature of these toxic ions, a redox reaction takes place between the framework metal ions and toxic metal ions, which is explained by an electron paramagnetic resonance study. This is the first report to synthesize non-toxic, as well as useful, NPs of As and Cr from their highly toxic ions within the cavities of a PCP for remediation of the toxic waste stream and contaminated waste water.

Use of a Card Sort Task to Assess Students' Ability to Coordinate Three Levels of Representation in Chemistry

ERIC Educational Resources Information Center

Irby, Stefan M.; Phu, Andy L.; Borda, Emily J.; Haskell, Todd R.; Steed, Nicole; Meyer, Zachary

2016-01-01

There is much agreement among chemical education researchers that expertise in chemistry depends in part on the ability to coordinate understanding of phenomena on three levels: macroscopic (observable), sub-microscopic (atoms, molecules, and ions) and symbolic (chemical equations, graphs, etc.). We hypothesize this "level-coordination…

Bis(μ-ferrocene­carboxyl­ato)bis­[aqua­­bis(ferrocene­carboxyl­ato)methano­l­erbium(III)] methanol disolvate

PubMed Central

Liu, Jianmin; Li, Yuanyuan; Li, Dacheng

2012-01-01

In the centrosymmetric title coordination compound, [Er2{Fe(C5H5)(C6H4O2)}6(CH3OH)2(H2O)2]·2CH3OH, the two ErIII ions are bridged by two ferrocene­carboxyl­ate anions as asymmetrically bridging ligands, leading to dimeric cores. The ErIII ion has a distorted dodeca­hedral coordination with six coordinating O atoms derived from the ferrocene­carboxyl­ate ligands and two coordinated O atoms from one water mol­ecule and one methanol mol­ecule. The asymmetric unit comprises a half of the complex mol­ecule and a methanol solvent mol­ecule. Intra­molecular O—H⋯O and C—H⋯O inter­actions occur. In the crystal, mol­ecules are linked by inter­molecular O—H⋯O hydrogen bonds and C—H⋯O as well as C—H⋯π inter­actions. PMID:22259358

Vibrational spectroscopy of metal methanesulfonates: M = Na, Cs, Cu, Ag, Cd

NASA Astrophysics Data System (ADS)

Parker, Stewart F.; Zhong, Lisha

2018-04-01

In this work, we have used a combination of vibrational spectroscopy (infrared, Raman and inelastic neutron scattering) and periodic density functional theory to investigate six metal methanesulfonate compounds that exhibit four different modes of complexation of the methanesulfonate ion: ionic, monodentate, bidentate and pentadentate. We found that the transition energies of the modes associated with the methyl group (C-H stretches and deformations, methyl rock and torsion) are essentially independent of the mode of coordination. The SO3 modes in the Raman spectra also show little variation. In the infrared spectra, there is a clear distinction between ionic (i.e. not coordinated) and coordinated forms of the methanesulfonate ion. This is manifested as a splitting of the asymmetric S-O stretch modes of the SO3 moiety. Unfortunately, no further differentiation between the various modes of coordination: unidentate, bidentate etc … is possible with the compounds examined. While it is likely that such a distinction could be made, this will require a much larger dataset of compounds for which both structural and spectroscopic data are available than that available here.

Binding ability of impromidine, a potent H2 agonist of histamine

NASA Astrophysics Data System (ADS)

Anouar, A.; Lhadi, E.; Decock, P.; Kozlowskyinst4, H.

1999-09-01

Impromidine (fig.1) is a potent and selective histamine H2 receptor agonist and its structure comprises a strongly basic guanidine group containing two different imidazole-containing side chains. The present work deals with the study of coordination equilibria between impromidine and Cu(II) and Ni(II) in aqueous solution at 25 circC. Potentiometric, UV-Visible and EPR studies on Cu(II) complexes with impromidine have shown that this anti-ulcerogenic drug is a very potent chelating agent. This drug is found to be a very effective ligand for Ni(II) ions also. The effective coordination of impromidine to metal ions may have significant biological implications. L'impromidine est un agoniste H2 de l'histamine, sa structure possède un groupement guanidinique de forte basicité et dont l'environne ment des deux groupements imidazoliques est différent. Le présent travail consiste en l'étude de la coordination de l'impromidine avec le Cu(II) et le Ni(II) en milieu aqueux à 25 circC. La potentiométrie, LíUV-Visible et la RPE montrent que le cuivre se coordine très fortement avec l'impromidine. Nous avons trouvé que ce médicament se coordine aussi fortement avec le nickel(II). La coordination de l'impromidine avec les métaux pourrait avoir des applications importantes en médecine.

Coordination-based gold nanoparticle layers.

PubMed

Wanunu, Meni; Popovitz-Biro, Ronit; Cohen, Hagai; Vaskevich, Alexander; Rubinstein, Israel

2005-06-29

Gold nanoparticle (NP) mono- and multilayers were constructed on gold surfaces using coordination chemistry. Hydrophilic Au NPs (6.4 nm average core diameter), capped with a monolayer of 6-mercaptohexanol, were modified by partial substitution of bishydroxamic acid disulfide ligand molecules into their capping layer. A monolayer of the ligand-modified Au NPs was assembled via coordination with Zr4+ ions onto a semitransparent Au substrate (15 nm Au, evaporated on silanized glass and annealed) precoated with a self-assembled monolayer of the bishydroxamate disulfide ligand. Layer-by-layer construction of NP multilayers was achieved by alternate binding of Zr4+ ions and ligand-modified NPs onto the first NP layer. Characterization by atomic force microscopy (AFM), ellipsometry, wettability, transmission UV-vis spectroscopy, and cross-sectional transmission electron microscopy showed regular growth of NP layers, with a similar NP density in successive layers and gradually increased roughness. The use of coordination chemistry enables convenient step-by-step assembly of different ligand-possessing components to obtain elaborate structures. This is demonstrated by introducing nanometer-scale vertical spacing between a NP layer and the gold surface, using a coordination-based organic multilayer. Electrical characterization of the NP films was carried out using conductive AFM, emphasizing the barrier properties of the organic spacer multilayer. The results exhibit the potential of coordination self-assembly in achieving highly controlled composite nanostructures comprising molecules, NPs, and other ligand-derivatized components.

Metal-Ion Effects on the Polarization of Metal-Bound Water and Infrared Vibrational Modes of the Coordinated Metal Center of Mycobacterium tuberculosis Pyrazinamidase via Quantum Mechanical Calculations

PubMed Central

2014-01-01

Mycobacterium tuberculosis pyrazinamidase (PZAse) is a key enzyme to activate the pro-drug pyrazinamide (PZA). PZAse is a metalloenzyme that coordinates in vitro different divalent metal cofactors in the metal coordination site (MCS). Several metals including Co2+, Mn2+, and Zn2+ are able to reactivate the metal-depleted PZAse in vitro. We use quantum mechanical calculations to investigate the Zn2+, Fe2+, and Mn2+ metal cofactor effects on the local MCS structure, metal–ligand or metal–residue binding energy, and charge distribution. Results suggest that the major metal-dependent changes occur in the metal–ligand binding energy and charge distribution. Zn2+ shows the highest binding energy to the ligands (residues). In addition, Zn2+ and Mn2+ within the PZAse MCS highly polarize the O–H bond of coordinated water molecules in comparison with Fe2+. This suggests that the coordination of Zn2+ or Mn2+ to the PZAse protein facilitates the deprotonation of coordinated water to generate a nucleophile for catalysis as in carboxypeptidase A. Because metal ion binding is relevant to enzymatic reaction, identification of the metal binding event is important. The infrared vibrational mode shift of the C=Nε (His) bond from the M. tuberculosis MCS is the best IR probe to metal complexation. PMID:25055049

Muonic molecular ions p p μ and p d μ driven by superintense VUV laser pulses: Postexcitation muonic and nuclear oscillations and high-order harmonic generation

NASA Astrophysics Data System (ADS)

Paramonov, Guennaddi K.; Saalfrank, Peter

2018-05-01

The non-Born-Oppenheimer quantum dynamics of p p μ and p d μ molecular ions excited by ultrashort, superintense VUV laser pulses polarized along the molecular axis (z ) is studied by the numerical solution of the time-dependent Schrödinger equation within a three-dimensional (3D) model, including the internuclear distance R and muon coordinates z and ρ , a transversal degree of freedom. It is shown that in both p p μ and p d μ , muons approximately follow the applied laser field out of phase. After the end of the laser pulse, expectation values , <ρ > , and demonstrate "post-laser-pulse" oscillations in both p p μ and p d μ . In the case of p d μ , the post-laser-pulse oscillations of and appear as shaped "echo pulses." Power spectra, which are related to high-order harmonic generation (HHG), generated due to muonic and nuclear motion are calculated in the acceleration form. For p d μ it is found that there exists a unique characteristic frequency ωoscp d μ representing both frequencies of post-laser-pulse muonic oscillations and the frequency of nuclear vibrations, which manifest themselves by very sharp maxima in the corresponding power spectra of p d μ . The homonuclear p p μ ion does not possess such a unique characteristic frequency. The "exact" dynamics and power, and HHG spectra of the 3D model are compared with a Born-Oppenheimer, fixed-nuclei model featuring interesting differences: postpulse oscillations are absent and HHG spectra are affected indirectly or directly by nuclear motion.

Spherical nonlinear ion-acoustic solitary waves in Titan's atmosphere

NASA Astrophysics Data System (ADS)

Selim, M. M.

2016-03-01

Propagation of spherical nonlinear ion-acoustic solitary waves in positive and negative ion plasmas with superthermal electrons is investigated. The effects of perturbations of the azimuthal and zenith-angle as well as the radial coordinate on the solitary wave profile are reported. The existence domains and the characteristics of the spherical solitary pulses are examined. The solitary excitations are found to be strongly dependent on the plasma parameters; the mass ratio of the positive-to-negative ions, electrons superthermality, and the spherical geometry. The role of superthermal electrons in formation of the spherical nonlinear ion-acoustic solitary excitations for two ion mass groups in Titan's upper atmosphere is investigated.

Spacelab energetic ion mass spectrometer

NASA Technical Reports Server (NTRS)

Whalen, B. A.; Mcdiarmid, I. B.; Burrows, J. R.; Sharp, R. D.; Johnson, R. G.; Shelley, E. G.

1980-01-01

Basic design criteria are given for an ion mass spectrometer for use in studying magnetospheric ion populations. The proposed instrument is composed of an electrostatic analyzer followed by a magnetic spectrometer and simultaneously measures the energy per unit and mass per unit charge of the ion species. An electromagnet is used for momentum analysis to extend the operational energy range over a much wider domain than is possible with the permanent magnets used in previous flights. The energetic ion source regions, ion energization mechanisms, field line tracing, coordinated investigations, and orbit considerations are discussed and operations of the momentum analyzer and of the electrostatic energy analyzer are examined.

Crystal structures of three lead(II) acetate-bridged di-amino-benzene coordination polymers.

PubMed

Geiger, David K; Parsons, Dylan E; Zick, Patricia L

2014-12-01

Poly[tris-(acetato-κ(2) O,O')(μ2-acetato-κ(3) O,O':O)tetra-kis-(μ3-acetato-κ(4) O,O':O:O')bis-(benzene-1,2-di-amine-κN)tetra-lead(II)], [Pb4(CH3COO)8(C6H8N2)2] n , (I), poly[(acetato-κ(2) O,O')(μ3-acetato-κ(4) O,O':O:O')(4-chloro-benzene-1,2-diamine-κN)lead(II)], [Pb(CH3COO)2(C6H7ClN2)] n , (II), and poly[(κ(2) O,O')(μ3-acetato-κ(4) O,O':O:O')(3,4-di-amino-benzo-nitrile-κN)lead(II)], [Pb(CH3COO)2(C7H7N3)] n , (III), have polymeric structures in which monomeric units are joined by bridging acetate ligands. All of the Pb(II) ions exhibit hemidirected coordination. The repeating unit in (I) is composed of four Pb(II) ions having O6, O6N, O7 and O6N coordination spheres, respectively, where N represents a monodentate benzene-1,2-di-amine ligand and O acetate O atoms. Chains along [010] are joined by bridging acetate ligands to form planes parallel to (10-1). (II) and (III) are isotypic and have one Pb(II) ion in the asymmetric unit that has an O6N coordination sphere. Pb2O2 units result from a symmetry-imposed inversion center. Polymeric chains parallel to [100] exhibit hydrogen bonding between the amine and acetate ligands. In (III), additional hydrogen bonds between cyano groups and non-coordinating amines join the chains by forming R 2 (2)(14) rings.

Synthesis, vibrational spectrometry and thermal characterizations of coordination polymers derived from divalent metal ions and hydroxyl terminated polyurethane as ligand

NASA Astrophysics Data System (ADS)

Laxmi; Khan, Shabnam; Kareem, Abdul; Zafar, Fahmina; Nishat, Nahid

2018-01-01

A series of novel coordination polyurethanes [HTPU-M, where M = Mn(II) 'd5', Ni(II) 'd8', and Zn(II) 'd10'] have been synthesized to investigate the effect of divalent metal ions coordination on structure, thermal and adsorption properties of low molecular weight hydroxyl terminated polyurethane (HTPU). HTPU-M have been synthesized in situ where, sbnd OH group of HTPU (synthesized by the condensation polymerization reaction of ethylene glycol (EG) and toluene diisocyanate (TDI) in presence of catalyst) on condensation polymerization with metal acetate in presence of acid catalyst synthesized HTPU-M followed by coordination of metal ions with hetero atoms. The structure, composition and geometry of HTPU-M have been confirmed by vibrational spectrometry (FTIR), 1H NMR, elemental analysis and UV-Visible spectroscopy. Morphological structures of HTPU-M were analyzed by X-Ray Diffraction analysis (XRD), Field Emission Scanning Electron Microscope (FE-SEM) with Energy Dispersive X-ray spectroscopy (EDX) and High Resolution Transmission Electron Microscope (HR-TEM) techniques. The thermal degradation pattern and thermal stability of HTPU-M in comparison to HTPU was investigated by thermal-gravimetric (TG)/differential thermal (DT), analyses along with Integral procedure decomposition temperature (IPDT) by Doyle method. The molecular weight of HTPU was determined by gel permeation chromatography (GPC). The preliminary adsorption/desorption studies of HTPU-M for Congo red (CR) was studied by batch adsorption techniques. The results indicated that HTPU-M have amorphous, layered morphology with higher number of nano-sized grooves in comparison to HTPU. Coordination of metal to HTPU plays a key role in enhancing the thermal stability [HTPU-Ni(II) > HTPU-Mn(II) > HTPU-Zn(II) > HTPU]. The HTPU-M can be utilized for industrial waste water treatment by removing environmental pollutants.

Dielectric relaxations and conduction mechanisms in polyether-clay composite polymer electrolytes under high carbon dioxide pressure.

PubMed

Kitajima, Shunsuke; Bertasi, Federico; Vezzù, Keti; Negro, Enrico; Tominaga, Yoichi; Di Noto, Vito

2013-10-21

The composite material P(EO/EM)-Sa consisting of synthetic saponite (Sa) dispersed in poly[ethylene oxide-co-2-(2-methoxyethoxy)ethyl glycidyl ether] (P(EO/EM)) is studied by "in situ" measurements using broadband electrical spectroscopy (BES) under pressurized CO2 to characterize the dynamic behavior of conductivity and the dielectric relaxations of the ion host polymer matrix. It is revealed that there are three dielectric relaxation processes associated with: (I) the dipolar motions in the short oxyethylene side chains of P(EO/EM) (β); and (II) the segmental motion of the main chains comprising the polyether components (αfast, αslow). αslow is attributed to the slow α-relaxation of P(EO/EM) macromolecules, which is hindered by the strong coordination interactions with the ions. Two conduction processes are observed, σDC and σID, which are attributed, respectively, to the bulk conductivity and the interdomain conductivity. The temperature dependence of conductivity and relaxation processes reveals that αfast and αslow are strongly correlated with σDC and σID. The "in situ" BES measurements under pressurized CO2 indicate a fast decrease in σDC at the initial CO2 treatment time resulting from the decrease in the concentration of polyether-M(n+) complexes, which is driven by the CO2 permeation. The relaxation frequency (fR) of αslow at the initial CO2 treatment time increases and shows a steep rise with time with the same behavior of the αfast mode. It is demonstrated that the interactions between polyether chains of P(EO/EM) and cations in the polymer electrolyte layers embedded in Sa are probably weakened by the low permittivity of CO2 (ε = 1.08). Thus, the formation of ion pairs in the polymer electrolyte domains of P(EO/EM)-Sa occurs, with a corresponding reduction in the concentration of ion carriers.

Dual motor drive vehicle speed synchronization and coordination control strategy

NASA Astrophysics Data System (ADS)

Huang, Hao; Tu, Qunzhang; Jiang, Chenming; Ma, Limin; Li, Pei; Zhang, Hongxing

2018-04-01

Multi-motor driven systems are more and more widely used in the field of electric engineering vehicles, as a result of the road conditions and the variable load of engineering vehicles, makes multi-motors synchronization coordinated control system as a key point of the development of the electric vehicle drive system. This paper based on electrical machinery transmission speed in the process of engineering vehicles headed for coordinated control problem, summarized control strategies at home and abroad in recent years, made analysis and comparison of the characteristics, finally discussed the trend of development of the multi-motor coordination control, provided a reference for synchronized control system research of electric drive engineering vehicles.

Nonlinear Electron and Ion Density Modulations Driven by Interfering High-Intensity Laser Pulses

NASA Astrophysics Data System (ADS)

Chen, S.; Zhang, P.; Saleh, N.; Sheng, Z. M.; Widjaja, C.; Umstadter, D.

2002-11-01

The optical spectrum from interaction of two crossed ultra short laser beams (400 fs) with underdense plasma is measured at various angles. Enhancement and broadening of the spectrum in the forward direction of one of the beams shows evidence of energy transfer between the two laser beams(G. Shvets, N. J. Fisch, A. Pukhov, and J. Meyer-ter-Vehn, Phys. Rev. E 60, 2218 (1999).), which is confirmed by a 2-D PIC simulation. The spectrum and scattered power indicate that a large amplitude electron density modulation is driven, which is attributed to the ponderomotive force of the interference, in agreement with simple analysis and simulation(δn/n_0>10). Stokes and anti-Stokes satellites reveals that the energy transfer is accompanied by a large amplitude nonlinear ion acoustic wave created by the laser interference in the strongly driven limit. The wavelength shift indicates that the ion acoustic wave's speed is 2.3×10^6m/s, corresponding to the electron temperature 119 keV, which is attributed to stochastic heating, also found in the simulation. Besides being of interest in basic plasma physics, this research is also relevant to fast igniter fusion or ion acceleration experiments, in which a laser pulse may potentially beat with a reflected weaker pulse, with intensities comparable to those used in the experiment(Y. Sentoku, et al., Appl. Phys. B 74, 207-215 (2002).).

Zonostrophic instability driven by discrete particle noise

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

St-Onge, D. A.; Krommes, J. A.

The consequences of discrete particle noise for a system possessing a possibly unstable collective mode are discussed. It is argued that a zonostrophic instability (of homogeneous turbulence to the formation of zonal flows) occurs just below the threshold for linear instability. The scenario provides a new interpretation of the random forcing that is ubiquitously invoked in stochastic models such as the second-order cumulant expansion or stochastic structural instability theory; neither intrinsic turbulence nor coupling to extrinsic turbulence is required. A representative calculation of the zonostrophic neutral curve is made for a simple two-field model of toroidal ion-temperature-gradient-driven modes. To themore » extent that the damping of zonal flows is controlled by the ion-ion collision rate, the point of zonostrophic instability is independent of that rate. Published by AIP Publishing.« less

Zonostrophic instability driven by discrete particle noise

DOE PAGES

St-Onge, D. A.; Krommes, J. A.

2017-04-01

The consequences of discrete particle noise for a system possessing a possibly unstable collective mode are discussed. It is argued that a zonostrophic instability (of homogeneous turbulence to the formation of zonal flows) occurs just below the threshold for linear instability. The scenario provides a new interpretation of the random forcing that is ubiquitously invoked in stochastic models such as the second-order cumulant expansion or stochastic structural instability theory; neither intrinsic turbulence nor coupling to extrinsic turbulence is required. A representative calculation of the zonostrophic neutral curve is made for a simple two-field model of toroidal ion-temperature-gradient-driven modes. To themore » extent that the damping of zonal flows is controlled by the ion-ion collision rate, the point of zonostrophic instability is independent of that rate. Published by AIP Publishing.« less

Electron/ion whistler instabilities and magnetic noise bursts

NASA Technical Reports Server (NTRS)

Akimoto, K.; Gary, S. Peter; Omidi, N.

1987-01-01

Two whistler instabilities are investigated by means of the linear Vlasov dispersion equation. They are called the electron/ion parallel and oblique whistler instabilities, and are driven by electron/ion relative drifts along the magnetic field. It is demonstrated that the enhanced fluctuations from these instabilities can explain several properties of magnetic noise bursts in and near the plasma sheet in the presence of ion beams and/or field-aligned currents. At sufficiently high plasma beta, these instabilities may affect the current system in the magnetotail.

Dispersion equation for electrostatic ion cyclotron instability under the effect of ionization in a dusty plasma

NASA Astrophysics Data System (ADS)

Singh, Sukhmander

2018-05-01

In the present paper we derive the plasma dispersion equation under the effect of ionization rate in a dust plasma to investigate the electrostatic ion cyclotron instability, where dust charge fluctuation is absent. It has one of the lowest threshold drift velocities among all the current-driven instabilities in isothermal plasma. The Electrostatic ion cyclotron instability in a dusty plasma containing electrons, light ions, and massive negatively charged dust grains which can be investigated both experimentally and theoretically.

Note: An inexpensive square waveform ion funnel driver

NASA Astrophysics Data System (ADS)

Hoffman, Nathan M.; Opačić, Bojana; Reilly, Peter T. A.

2017-01-01

An inexpensive frequency variable square waveform generator (WFG) was developed to use with existing sinusoidal waveform driven ion funnels. The developed WFG was constructed using readily available low voltage DC power supplies and discrete components placed in printed circuit boards. As applied to ion funnels, this WFG represents considerable cost savings over commercially available products without sacrificing performance. Operation of the constructed pulse generator has been demonstrated for a 1 nF ion funnel at an operating frequency of 1 MHz while switching 48 Vp-p.

Note: An inexpensive square waveform ion funnel driver.

PubMed

Hoffman, Nathan M; Opačić, Bojana; Reilly, Peter T A

2017-01-01

An inexpensive frequency variable square waveform generator (WFG) was developed to use with existing sinusoidal waveform driven ion funnels. The developed WFG was constructed using readily available low voltage DC power supplies and discrete components placed in printed circuit boards. As applied to ion funnels, this WFG represents considerable cost savings over commercially available products without sacrificing performance. Operation of the constructed pulse generator has been demonstrated for a 1 nF ion funnel at an operating frequency of 1 MHz while switching 48 V p-p .

The lanthanide contraction beyond coordination chemistry

DOE PAGES

Ferru, Geoffroy; Reinhart, Benjamin; Bera, Mrinal K.; ...

2016-04-06

Lanthanide chemistry is dominated by the ‘lanthanide contraction’, which is conceptualized traditionally through coordination chemistry. Here we break this mold, presenting evidence that the lanthanide contraction manifests outside of the coordination sphere, influencing weak interactions between groups of molecules that drive mesoscale-assembly and emergent behavior in an amphiphile solution. Furthermore, changes in these weak interactions correlate with differences in lanthanide ion transport properties, suggesting new forces to leverage rare earth separation and refining. Our results show that the lanthanide contraction paradigm extends beyond the coordination sphere, influencing structure and properties usually associated with soft matter science.

The lanthanide contraction beyond coordination chemistry

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

Ferru, Geoffroy; Reinhart, Benjamin; Bera, Mrinal K.

Lanthanide chemistry is dominated by the ‘lanthanide contraction’, which is conceptualized traditionally through coordination chemistry. Here we break this mold, presenting evidence that the lanthanide contraction manifests outside of the coordination sphere, influencing weak interactions between groups of molecules that drive mesoscale-assembly and emergent behavior in an amphiphile solution. Furthermore, changes in these weak interactions correlate with differences in lanthanide ion transport properties, suggesting new forces to leverage rare earth separation and refining. Our results show that the lanthanide contraction paradigm extends beyond the coordination sphere, influencing structure and properties usually associated with soft matter science.

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

Ren, Aiming; Rajashankar, Kanagalaghatta R.; Patel, Dinshaw J.

Significant advances in our understanding of RNA architecture, folding and recognition have emerged from structure-function studies on riboswitches, non-coding RNAs whose sensing domains bind small ligands and whose adjacent expression platforms contain RNA elements involved in the control of gene regulation. We now report on the ligand-bound structure of the Thermotoga petrophila fluoride riboswitch, which adopts a higher-order RNA architecture stabilized by pseudoknot and long-range reversed Watson-Crick and Hoogsteen A {sm_bullet} U pair formation. The bound fluoride ion is encapsulated within the junctional architecture, anchored in place through direct coordination to three Mg{sup 2+} ions, which in turn are octahedrallymore » coordinated to water molecules and five inwardly pointing backbone phosphates. Our structure of the fluoride riboswitch in the bound state shows how RNA can form a binding pocket selective for fluoride, while discriminating against larger halide ions. The T. petrophila fluoride riboswitch probably functions in gene regulation through a transcription termination mechanism.« less

Comparison of different substrates for laser-induced electron transfer desorption/ionization of metal complexes

NASA Astrophysics Data System (ADS)

Grechnikov, A. A.; Georgieva, V. B.; Donkov, N.; Borodkov, A. S.; Pento, A. V.; Raicheva, Z. G.; Yordanov, Tc A.

2016-03-01

Four different substrates, namely, graphite, tungsten, amorphous silicon (α-Si) and titanium dioxide (TiO2) films, were compared in view of the laser-induced electron transfer desorption/ionization (LETDI) of metal coordination complexes. A rhenium complex with 8-mercaptoquinoline, a copper complex with diphenylthiocarbazone and chlorophyll A were studied as the test analytes. The dependencies of the ion yield and the surface temperature on the incident radiation fluence were investigated experimentally and theoretically. The temperature was estimated using the numerical solution of a one-dimensional heat conduction problem with a heat source distributed in time and space. It was found that at the same temperature, the ion yield from the different substrates varies in the range of three orders of magnitude. The direct comparison of all studied substrates revealed that LETDI from the TiO2 and α-Si films offer a better choice for producing molecular ions of metal coordination complexes.

UV-visible, Raman and E.S.R. studies of gamma-irradiated NiO-doped sodium metaphosphate glasses.

PubMed

ElBatal, Fatma H; Morsi, Reham M; Ouis, Mona A; Marzouk, Samir Y

2010-11-01

UV-visible spectroscopic measurements of Ni-doped sodium phosphate glasses were carried out before and after successive gamma irradiation. The undoped glass reveals strong UV absorption originating from trace iron impurities. NiO-doped glasses show characteristic absorption bands due mainly to octahedral coordination of Ni(2+) ions. Gamma irradiation produces induced bands generated from intrinsic defects and extrinsic defects. The changes in the spectroscopic data are discussed in relation to the structural evolution caused by the changes in composition and coordination state of nickel ions. The change in the growth behaviour of the induced bands is related to the annihilation or approach saturation of these characteristic induced bands. Raman and E.S.R. spectroscopic measurements confirm the presence of nickel as Ni(2+) ions in octahedral state. Copyright © 2010 Elsevier B.V. All rights reserved.

NMR spectroscopy of Group 13 metal ions: biologically relevant aspects.

PubMed

André, J P; Mäcke, H R

2003-12-01

In spite of the fact that Group 13 metal ions (Al(3+), Ga(3+), In(3+) and Tl(+/3+)) show no main biological role, they are NMR-active nuclides which can be used in magnetic resonance spectroscopy of biologically relevant systems. The fact that these metal ions are quadrupolar (with the exception of thallium) means that they are particularly sensitive to ligand type and coordination geometry. The line width of the NMR signals of their complexes shows a strong dependence on the symmetry of coordination, which constitutes an effective tool in the elucidation of structures. Here we report published NMR studies of this family of elements, applied to systems of biological importance. Special emphasis is given to binding studies of these cations to biological molecules, such as proteins, and to chelating agents of radiopharmaceutical interest. The possibility of in vivo NMR studies is also stressed, with extension to (27)Al-based MRI (magnetic resonance imaging) experiments.

Toward the understanding of hydration phenomena in aqueous electrolytes from the interplay of theory, molecular simulation, and experiment

DOE PAGES

Chialvo, Ariel A.; Vlcek, Lukas

2015-05-22

We confront the microstructural analysis of aqueous electrolytes and present a detailed account of the fundamentals underlying the neutron scattering with isotopic substitution (NDIS) approach for the experimental determination of ion coordination numbers in systems involving both halides anions and oxyanions. We place particular emphasis on the frequently overlooked ion-pairing phenomenon, identify its microstructural signature in the neutron-weighted distribution functions, and suggest novel techniques to deal with either the estimation of the ion-pairing magnitude or the correction of its effects on the experimentally measured coordination numbers. We illustrate the underlying ideas by applying these new developments to the interpretation ofmore » four NDIS test-cases via molecular simulation, as convenient dry runs for the actual scattering experiments, for representative aqueous electrolyte solutions at ambient conditions involving metal halides and nitrates.« less

A conserved residue, PomB-F22, in the transmembrane segment of the flagellar stator complex, has a critical role in conducting ions and generating torque.

PubMed

Terauchi, Takashi; Terashima, Hiroyuki; Kojima, Seiji; Homma, Michio

2011-08-01

Bacterial flagellar motors exploit the electrochemical potential gradient of a coupling ion (H(+) or Na(+)) as their energy source, and are composed of stator and rotor proteins. Sodium-driven and proton-driven motors have the stator proteins PomA and PomB or MotA and MotB, respectively, which interact with each other in their transmembrane (TM) regions to form an ion channel. The single TM region of PomB or MotB, which forms the ion-conduction pathway together with TM3 and TM4 of PomA or MotA, respectively, has a highly conserved aspartate residue that is the ion binding site and is essential for rotation. To investigate the ion conductivity and selectivity of the Na(+)-driven PomA/PomB stator complex, we replaced conserved residues predicted to be near the conserved aspartate with H(+)-type residues, PomA-N194Y, PomB-F22Y and/or PomB-S27T. Motility analysis revealed that the ion specificity was not changed by either of the PomB mutations. PomB-F22Y required a higher concentration of Na(+) to exhibit swimming, but this effect was suppressed by additional mutations, PomA-N194Y or PomB-S27T. Moreover, the motility of the PomB-F22Y mutant was resistant to phenamil, a specific inhibitor for the Na(+) channel. When PomB-F22 was changed to other amino acids and the effects on swimming ability were investigated, replacement with a hydrophilic residue decreased the maximum swimming speed and conferred strong resistance to phenamil. From these results, we speculate that the Na(+) flux is reduced by the PomB-F22Y mutation, and that PomB-F22 is important for the effective release of Na(+) from PomB-D24.

Vanadium-pumped titanium x-ray laser

DOEpatents

Nilsen, J.

1992-05-26

A resonantly photo-pumped x-ray laser is formed of a vanadium and titanium foil combination that is driven by two beams of intense line focused optical laser radiation. Ground state neon-like titanium ions are resonantly photo-pumped by line emission from fluorine-like vanadium ions. 4 figs.

Synthesis and thermal characterization of new ternary chelates of piroxicam and tenoxicam with glycine and DL-phenylalanine and some transition metals.

PubMed

Zayed, M A; El-Dien, F A Nour; Mohamed, Gehad G; El-Gamel, Nadia E A

2006-05-01

The ternary chelates of piroxicam (Pir) and tenoxicam (Ten) with Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) in the presence of various amino acids such as glycine (Gly) or dl-phenylalanine (PhA) were prepared and characterized with different physicochemical methods. IR spectra confirm that Pir and Ten behave as a neutral bidentate ligand coordinated to the metal ions via the pyridine-N and carbonyl group of the amide moiety. Gly molecule acted as a uninegatively monodentate ligand and coordinate to the metal ions through its deprotonated carboxylic group. In addition, PhA acted as a uninegatively bidentate ligand and coordinate to the metal ions through its deprotonated carboxylic and amino groups. The solid reflectance spectra and magnetic moment measurements confirm that all the chelates have octahedral geometrical structures while Cu(II)- and Zn(II)-ternary chelates with PhA have square planar geometrical structures. Thermal behaviour of the complexes is extensively studied using TG and DTA techniques. TG results show that water molecules (hydrated and coordinated) and anions are removed in the first and second steps while Gly, PhA, Pir and Ten are decomposed in the next and subsequent steps. The pyrolyses of the chelates into different gases are observed in the DTA curves as exo- or endothermic peaks. Also, phase transition states are observed in some chelates. Different thermodynamic parameters are calculated using Coats-Redfern method and the results are interpreted.

Synthesis and thermal characterization of new ternary chelates of piroxicam and tenoxicam with glycine and DL-phenylalanine and some transition metals

NASA Astrophysics Data System (ADS)

Zayed, M. A.; El-Dien, F. A. Nour; Mohamed, Gehad G.; El-Gamel, Nadia E. A.

2006-05-01

The ternary chelates of piroxicam (Pir) and tenoxicam (Ten) with Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) in the presence of various amino acids such as glycine (Gly) or DL-phenylalanine (PhA) were prepared and characterized with different physicochemical methods. IR spectra confirm that Pir and Ten behave as a neutral bidentate ligand coordinated to the metal ions via the pyridine- N and carbonyl group of the amide moiety. Gly molecule acted as a uninegatively monodentate ligand and coordinate to the metal ions through its deprotonated carboxylic group. In addition, PhA acted as a uninegatively bidentate ligand and coordinate to the metal ions through its deprotonated carboxylic and amino groups. The solid reflectance spectra and magnetic moment measurements confirm that all the chelates have octahedral geometrical structures while Cu(II)- and Zn(II)-ternary chelates with PhA have square planar geometrical structures. Thermal behaviour of the complexes is extensively studied using TG and DTA techniques. TG results show that water molecules (hydrated and coordinated) and anions are removed in the first and second steps while Gly, PhA, Pir and Ten are decomposed in the next and subsequent steps. The pyrolyses of the chelates into different gases are observed in the DTA curves as exo- or endothermic peaks. Also, phase transition states are observed in some chelates. Different thermodynamic parameters are calculated using Coats-Redfern method and the results are interpreted.

Studies on the Extraction Region of the Type VI RF Driven H- Ion Source

NASA Astrophysics Data System (ADS)

McNeely, P.; Bandyopadhyay, M.; Franzen, P.; Heinemann, B.; Hu, C.; Kraus, W.; Riedl, R.; Speth, E.; Wilhelm, R.

2002-11-01

IPP Garching has spent several years developing a RF driven H- ion source intended to be an alternative to the current ITER (International Thermonuclear Experimental Reactor) reference design ion source. A RF driven source offers a number of advantages to ITER in terms of reduced costs and maintenance requirements. Although the RF driven ion source has shown itself to be competitive with a standard arc filament ion source for positive ions many questions still remain on the physics behind the production of the H- ion beam extracted from the source. With the improvements that have been implemented to the BATMAN (Bavarian Test Machine for Negative Ions) facility over the last two years it is now possible to study both the extracted ion beam and the plasma in the vicinity of the extraction grid in greater detail. This paper will show the effect of changing the extraction and acceleration voltage on both the current and shape of the beam as measured on the calorimeter some 1.5 m downstream from the source. The extraction voltage required to operate in the plasma limit is 3 kV. The perveance optimum for the extraction system was determined to be 2.2 x 10-6 A/V3/2 and occurs at 2.7 kV extraction voltage. The horizontal and vertical beam half widths vary as a function of the extracted ion current and the horizontal half width is generally smaller than the vertical. The effect of reducing the co-extracted electron current via plasma grid biasing on the H- current extractable and the beam profile from the source is shown. It is possible in the case of a silver contaminated plasma to reduce the co-extracted electron current to 20% of the initial value by applying a bias of 12 V. In the case where argon is present in the plasma, biasing is observed to have minimal effect on the beam half width but in a pure hydrogen plasma the beam half width increases as the bias voltage increases. New Langmuir probe studies that have been carried out parallel to the plasma grid (in the vicinity of the peak of the external magnetic filter field) and changes to source parameters as a function of power, and argon addition are reported. The behaviour of the electron density is different when the plasma is argon seeded showing a strong increase with RF power. The plasma potential is decreased by 2 V when argon is added to the plasma. The effect of the presence of unwanted silver sputtered from the Faraday screen by Ar+ ions on both the source performance and the plasma parameters is also presented. The silver dramatically downgraded source performance in terms of current density and produced an early saturation of current with applied RF power. Recently, collaboration was begun with the Technical University of Augsburg to perform spectroscopic measurements on the Type VI ion source. The final results of this analysis are not yet ready but some interesting initial observations on the gas temperature, disassociation degree and impurity ions will be presented.

Photocatalytic activity of PANI loaded coordination polymer composite materials: Photoresponse region extension and quantum yields enhancement via the loading of PANI nanofibers on surface of coordination polymer

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

Cui, Zhongping; Qi, Ji; Xu, Xinxin, E-mail: xuxx@mail.neu.edu.cn

2013-09-15

To enhance photocatalytic property of coordination polymer in visible light region, polyaniline (PANI) loaded coordination polymer photocatalyst was synthesized through in-situ chemical oxidation of aniline on the surface of coordination polymer. The photocatalytic activity of PANI loaded coordination polymer composite material for degradation of Rhodamine B (RhB) was investigated. Compared with pure coordination polymer photocatalyst, which can decompose RhB merely under UV light irradiation, PANI loaded coordination polymer photocatalyst displays more excellent photocatalytic activity in visible light region. Furthermore, PANI loaded coordination polymer photocatalyst exhibits outstanding stability during the degradation of RhB. - Graphical abstract: PANI loaded coordination polymer compositemore » material, which displays excellent photocatalytic activity under visible light was firstly synthesized through in-situ chemical oxidation of aniline on surface of coordination polymer. Display Omitted - Highlights: • This PANI loaded coordination polymer composite material represents the first conductive polymer loaded coordination polymer composite material. • PANI/coordination polymer composite material displays more excellent photocatalytic activity for the degradation of MO in visible light region. • The “combination” of coordination polymer and PANI will enable us to design high-activity, high-stability and visible light driven photocatalyst in the future.« less

Structural influence of mixed transition metal ions on lithium bismuth borate glasses

NASA Astrophysics Data System (ADS)

Yadav, Arti; Dahiya, Manjeet S.; Hooda, A.; Chand, Prem; Khasa, S.

2017-08-01

Lithium bismuth borate glasses containing mixed transition metals having composition 7CoO·23Li2O·20Bi2O3·50B2O3 (CLBB), 7V2O5·23Li2O·20Bi2O3·50B2O3 (VLBB) and x(2CoO·V2O5)·(30 - x)Li2O·20Bi2O3·50B2O3 (x = 0.0 (LBB) and x = 2.0, 5.0, 7.0, 10.0 mol% (CVLBB1-4)) are synthesized via melt quench route. The synthesized compositions are investigated for their physical properties using density (D) and molar volume (Vm), thermal properties by analyzing DSC/TG thermo-graphs, structural properties using IR absorption spectra in the mid-IR range and optical properties using UV-Vis-NIR spectroscopy. The Electron Paramagnetic Resonance (EPR) spectra of vanadyl and cobalt ion have been analyzed to study compositional effects on spin-Hamiltonian parameters. The non linear variations in physical properties depict a strong structural influence of Co/V- oxides on the glassy matrix. The compositional variations in characteristic temperatures (glass transition temperature Tg, glass crystallization temperature Tp and glass melting temperature Tm) reveals that Tg for glass samples CLBB is relatively less than that of pure lithium bismuth borate (LBB) glass sample wherein Tg for sample VLBB is higher than that of LBB. The increase in Tg (as compared with LBB) with an enhanced substitution of mixed transition metal oxides (2CoO·V2O5) shows a progressive structure modification of bismuth borate matrix. These predictions are very well corroborated by corresponding compositional trends of Tp and Tm. FTIR studies reveal that Co2+& VO2+ ions lead to structural rearrangements through the conversion of three-coordinated boron into four coordinated boron and thereby reducing number of non-bridging oxygen atoms. Bismuth is found to exist in [BiO6] octahedral units only, whereas boroxol rings are not present in the glass network. The theoretical values of optical basicity (Λth) and corresponding oxide ion polarizability (αo2-) have also been calculated to investigate oxygen covalency of glass matrix. Trends in both these parameters suggested an increase in ionic bonding on substitution of divalent transition metal cations causing a more bonding compaction in glass structure. The UV-Vis-NIR spectra suggest that cobalt ions exist as Co2+ states in octahedral coordination in glass network. Inter-electronic repulsion parameter and crystal field splitting energy were evaluated to understand the site symmetry around Co2+-ion in glass. X-band EPR spectra suggest that vanadium ions (V4+) exists as VO2+-ions in octahedral coordination with tetragonal compression. Spin Hamiltonian parameters g-values and A-values of VO2+ ions in glass were calculated. For sample CLBB two resonance lines in EPR spectrum attribute to octahedral symmetry around Co2+-ions were observed.

Small-angle neutron scattering study of specific interaction and coordination structure formed by mono-acetyl-substituted dibenzo-20-crown-6-ether and cesium ions

DOE PAGES

Motokawa, Ryuhei; Kobayashi, Tohru; Endo, Hitoshi; ...

2015-10-26

This study uses small-angle neutron scattering (SANS) to elucidate the coordination structure of the complex of mono-acetyl-substituted dibenzo-20-crown-6-ether (ace-DB20C6) with cesium ions (Cs +). SANS profiles obtained for the complex of ace-DB20C6 and Cs + (ace-DB20C6/Cs) in deuterated dimethyl sulfoxide indicated that Cs + coordination resulted in a more compact structure than the free ace-DB20C6. The data were fitted well with SANS profiles calculated using Debye function for scattering on an absolute scattering intensity scale. For this theoretical calculation of the scattering profiles, the coordination structure proposed based on density functional theory calculation was used. Furthermore, we conclude that themore » SANS analysis experimentally supports the proposed coordination structure of ace-DB20C6/Cs and suggests the following: (1) the complex of ace-DB20C6 and Cs + is formed with an ace-DB20C6/Cs molar ratio of 1/1 and (2) the two benzene rings of ace-DB20C6 fold around Cs + above the center of the crown ether ring of ace-DB20C6.« less

Small-angle neutron scattering study of specific interaction and coordination structure formed by mono-acetyl-substituted dibenzo-20-crown-6-ether and cesium ions

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

Motokawa, Ryuhei; Kobayashi, Tohru; Endo, Hitoshi

This study uses small-angle neutron scattering (SANS) to elucidate the coordination structure of the complex of mono-acetyl-substituted dibenzo-20-crown-6-ether (ace-DB20C6) with cesium ions (Cs +). SANS profiles obtained for the complex of ace-DB20C6 and Cs + (ace-DB20C6/Cs) in deuterated dimethyl sulfoxide indicated that Cs + coordination resulted in a more compact structure than the free ace-DB20C6. The data were fitted well with SANS profiles calculated using Debye function for scattering on an absolute scattering intensity scale. For this theoretical calculation of the scattering profiles, the coordination structure proposed based on density functional theory calculation was used. Furthermore, we conclude that themore » SANS analysis experimentally supports the proposed coordination structure of ace-DB20C6/Cs and suggests the following: (1) the complex of ace-DB20C6 and Cs + is formed with an ace-DB20C6/Cs molar ratio of 1/1 and (2) the two benzene rings of ace-DB20C6 fold around Cs + above the center of the crown ether ring of ace-DB20C6.« less

Synthesis, crystal structure, and luminescent properties of two coordination polymers based on 1,4-phenylenediacetic acid

NASA Astrophysics Data System (ADS)

Zhang, Meili; Ren, Yixia; Ma, Zhenzhen; Qiao, Lei

2017-06-01

Two coordination polymers, [Zn(pda)(bib)]n (1) and [Cd(pda)0.5(bib)Cl]n (2)]. (H2pda = 1,4-phenylenediacetic acid, bib = 1,2-bis(imidazol-1-ylmethyl)benzene), have been synthesized by using Zn(II)/Cd(II) salts with two flexible ligands pda and bib under hydrothermal conditions. Their structures have been characterized by elemental analysis, IR spectroscopy, single-crystal X-ray crystallography and powder X-ray diffraction (PXRD) analysis. Due to the coordination geometry around the metal ions and the diverse coordination modes of the flexible ligands, the obtained complex show diverse structures. In the structure of 1, a pair of bib ligands connect two Zn(II) atoms give rise a 22-membered ring, which is further extended by pda ligands in bidentate coordination mode leading a ring-containing 2D layer. In 2, bib ligands join [Cd2Cl2]2+ dimmers generate 1D polymeric ribbon, the pda ligands further extend such ribbon forming a 2D layer network containing rectangular windows, which discovers the effect of the central metal ions on the formation of metal-organic frameworks. In additional, luminescent properties of two complexes have also been studied, they could be potential fluorescence materials.

Microcompartments and Protein Machines in Prokaryotes

PubMed Central

Saier, Milton H.

2013-01-01

The prokaryotic cell was once thought of as a “bag of enzymes” with little or no intracellular compartmentalization. In this view, most reactions essential for life occurred as a consequence of random molecular collisions involving substrates, cofactors and cytoplasmic enzymes. Our current conception of a prokaryote is far from this view. We now consider a bacterium or an archaeon as a highly structured, non-random collection of functional membrane-embedded and proteinaceous molecular machines, each of which serves a specialized function. In this article we shall present an overview of such microcompartments including (i) the bacterial cytoskeleton and the apparati allowing DNA segregation during cells division, (ii) energy transduction apparati involving light-driven proton pumping and ion gradient-driven ATP synthesis, (iii) prokaryotic motility and taxis machines that mediate cell movements in response to gradients of chemicals and physical forces, (iv) machines of protein folding, secretion and degradation, (v) metabolasomes carrying out specific chemical reactions, (vi) 24 hour clocks allowing bacteria to coordinate their metabolic activities with the daily solar cycle and (vii) proteinaceous membrane compartmentalized structures such as sulfur granules and gas vacuoles. Membrane-bounded prokaryotic organelles were considered in a recent JMMB written symposium concerned with membraneous compartmentalization in bacteria [Saier and Bogdanov, 2013]. By contrast, in this symposium, we focus on proteinaceous microcompartments. These two symposia, taken together, provide the interested reader with an objective view of the remarkable complexity of what was once thought of as a simple non-compartmentalized cell. PMID:23920489

K(+)-Induced in situ self-assembly of near-infrared luminescent membrane material armored with bigger Yb(III) complex crystallites.

PubMed

Chen, Wanmin; Tang, Xiaoliang; Dou, Wei; Ju, Zhenghua; Xu, Benhua; Xu, Wenxuan; Liu, Weisheng

2016-04-14

A semi-rigid ligand could capture effectively Yb(3+) ions to form a stable Yb(3+) complex and provide a potential cavity to accommodate alkali metal ions. Only K(+) ions could induce the Yb(3+) complex to form a 1D coordination polymer and promote the in situ formation of an NIR membrane coated with bigger Yb(3+) complex crystallites under mild conditions.

Effects-Driven Participatory Design: Learning from Sampling Interruptions.

PubMed

Brandrup, Morten; Østergaard, Kija Lin; Hertzum, Morten; Karasti, Helena; Simonsen, Jesper

2017-01-01

Participatory design (PD) can play an important role in obtaining benefits from healthcare information technologies, but we contend that to fulfil this role PD must incorporate feedback from real use of the technologies. In this paper we describe an effects-driven PD approach that revolves around a sustained focus on pursued effects and uses the experience sampling method (ESM) to collect real-use feedback. To illustrate the use of the method we analyze a case that involves the organizational implementation of electronic whiteboards at a Danish hospital to support the clinicians' intra- and interdepartmental coordination. The hospital aimed to reduce the number of phone calls involved in coordinating work because many phone calls were seen as unnecessary interruptions. To learn about the interruptions we introduced an app for capturing quantitative data and qualitative feedback about the phone calls. The investigation showed that the electronic whiteboards had little potential for reducing the number of phone calls at the operating ward. The combination of quantitative data and qualitative feedback worked both as a basis for aligning assumptions to data and showed ESM as an instrument for triggering in-situ reflection. The participant-driven design and redesign of the way data were captured by means of ESM is a central contribution to the understanding of how to conduct effects-driven PD.

Recent advances in laser-driven neutron sources

NASA Astrophysics Data System (ADS)

Alejo, A.; Ahmed, H.; Green, A.; Mirfayzi, S. R.; Borghesi, M.; Kar, S.

2016-11-01

Due to the limited number and high cost of large-scale neutron facilities, there has been a growing interest in compact accelerator-driven sources. In this context, several potential schemes of laser-driven neutron sources are being intensively studied employing laser-accelerated electron and ion beams. In addition to the potential of delivering neutron beams with high brilliance, directionality and ultra-short burst duration, a laser-driven neutron source would offer further advantages in terms of cost-effectiveness, compactness and radiation confinement by closed-coupled experiments. Some of the recent advances in this field are discussed, showing improvements in the directionality and flux of the laser-driven neutron beams.

Sparkle model for the calculation of lanthanide complexes: AM1 parameters for Eu(III), Gd(III), and Tb(III).

PubMed

Freire, Ricardo O; Rocha, Gerd B; Simas, Alfredo M

2005-05-02

Our previously defined Sparkle model (Inorg. Chem. 2004, 43, 2346) has been reparameterized for Eu(III) as well as newly parameterized for Gd(III) and Tb(III). The parameterizations have been carried out in a much more extensive manner, aimed at producing a new, more accurate model called Sparkle/AM1, mainly for the vast majority of all Eu(III), Gd(III), and Tb(III) complexes, which possess oxygen or nitrogen as coordinating atoms. All such complexes, which comprise 80% of all geometries present in the Cambridge Structural Database for each of the three ions, were classified into seven groups. These were regarded as a "basis" of chemical ambiance around a lanthanide, which could span the various types of ligand environments the lanthanide ion could be subjected to in any arbitrary complex where the lanthanide ion is coordinated to nitrogen or oxygen atoms. From these seven groups, 15 complexes were selected, which were defined as the parameterization set and then were used with a numerical multidimensional nonlinear optimization to find the best parameter set for reproducing chemical properties. The new parameterizations yielded an unsigned mean error for all interatomic distances between the Eu(III) ion and the ligand atoms of the first sphere of coordination (for the 96 complexes considered in the present paper) of 0.09 A, an improvement over the value of 0.28 A for the previous model and the value of 0.68 A for the first model (Chem. Phys. Lett. 1994, 227, 349). Similar accuracies have been achieved for Gd(III) (0.07 A, 70 complexes) and Tb(III) (0.07 A, 42 complexes). Qualitative improvements have been obtained as well; nitrates now coordinate correctly as bidentate ligands. The results, therefore, indicate that Eu(III), Gd(III), and Tb(III) Sparkle/AM1 calculations possess geometry prediction accuracies for lanthanide complexes with oxygen or nitrogen atoms in the coordination polyhedron that are competitive with present day ab initio/effective core potential calculations, while being hundreds of times faster.

Role of the Zn1 and Zn2 sites in metallo-β-lactamase L1

PubMed Central

Hu, Zhenxin; Periyannan, Gopalraj; Bennett, Brian; Crowder, Michael W.

2009-01-01

In an effort to probe the role of the Zn(II) sites in metallo-β-lactamase L1, mononuclear metal ion containing and heterobimetallic analogs of the enzyme were generated and characterized using kinetic and spectroscopic studies. Mononuclear Zn(II)-containing L1, which binds Zn(II) in the consensus Zn1 site, was shown to be slightly active; however, this enzyme did not stabilize a nitrocefin-derived reaction intermediate that had been previously detected. Mononuclear Co(II)- and Fe(III)-containing L1 were essentially inactive, and NMR and EPR studies suggest that these metal ions bind to the consensus Zn2 site in L1. Heterobimetallic analogs (ZnCo and ZnFe) analogs of L1 were generated, and stopped-flow kinetic studies revealed that these enzymes rapidly hydrolyze nitrocefin and that there are large amounts of the reaction intermediate formed during the reaction. The heterobimetallic analogs were reacted with nitrocefin, and the reactions were rapidly freeze quenched. EPR studies on these samples demonstrate that Co(II) is five-coordinate in the resting state, proceeds through a four-coordinate species during the reaction, and is five-coordinate in the enzyme-product complex. These studies demonstrate that the metal ion in the Zn1 site is essential for catalysis in L1 and that the metal ion in the Zn2 site is crucial for stabilization of the nitrocefin-derived reaction intermediate. PMID:18831550

A novel smart supramolecular organic gelator exhibiting dual-channel responsive sensing behaviours towards fluoride ion via gel-gel states.

PubMed

Mehdi, Hassan; Pang, Hongchang; Gong, Weitao; Dhinakaran, Manivannan Kalavathi; Wajahat, Ali; Kuang, Xiaojun; Ning, Guiling

2016-07-07

A novel smart supramolecular organic gelator G-16 containing anion and metal-coordination ability has been designed and synthesized. It shows excellent and robust gelation capability as a strong blue fluorescent supramolecular organic gel OG in DMF. Addition of Zn(2+) produced Zn(2+)-coordinated supramolecular metallogel OG-Zn. Organic gel OG and organometallic gel OG-Zn exhibited efficient and different sensing behaviors towards fluoride ion due to the variation in self-assembling nature. Supramolecular metallogel OG-Zn displayed specific selectivity for fluoride ion and formed OG-Zn-F with dramatic color change from blue to blue green in solution and gel to gel states. Furthermore after directly addition of fluoride into OG produced fluoride containing organic gel OG-F with drastically modulation in color from blue to greenish yellow fluorescence via strong aggregation-induced emission (AIE) property. A number of experiments were conducted such as FTIR, (1)H NMR, and UV/Vis spectroscopies, XRD, SEM and rheology. These results revealed that the driving forces involved in self-assembly of OG, OG-Zn, OG-Zn-F and OG-F were hydrogen bonding, metal coordination, π-π interactions, and van der Waal forces. In contrast to the most anion responsive gels, particularly fluoride ion responsive gels showed gel-sol state transition on stimulation by anions, the gel state of OG and OG-Zn did not show any gel-to-sol transition during the whole F(-) response process.

One- and two-electron reduced 1,2-diketone ligands in [CrIII(L*)3] (S = 0) and Na2(Et2O)2[VIV(LRed)3] (S = 1/2).

PubMed

Spikes, Geoffrey H; Sproules, Stephen; Bill, Eckhard; Weyhermüller, Thomas; Wieghardt, Karl

2008-12-01

The electronic structures of chromium and vanadium centers coordinated by three reduced 1,2-diketones have been elucidated by using density functional theory (DFT) calculations and a host of physical methods: X-ray crystallography; cyclic voltammetry; ultraviolet-visible (UV-vis), nuclear magnetic resonance (NMR), and electron paramagnetic resonance (EPR) spectroscopy; and magnetic susceptibility measurements. The metal center in octahedral [CrIII(L*)3]0 (1), a CrIII (d3) ion is coupled antiferromagnetically to three monoanionic ligand pi-radicals affording an S ) 0 ground state. In contrast, Na2(Et2O)2[VIV(LRed)3] (2) (S ) 1/2), possesses a central VIV (d1) ion O,OE-coordinated to three closed-shell, doubly reduced ligands which in turn are coordinated by two Na cations enforcing a trigonal prismatic geometry at the vanadium center. 2 can be oxidized electrochemically by one and two electrons generating a monoanion, [V(L)3]1-, and a neutral species, [V(L)3]0, respectively. DFT calculations atthe B3LYP level show that the one-electron oxidized product contains an octahedral VIV ion coupled antiferromagnetically to one monoanionic ligand pi-radical [VIV(L*)(LRed)2]1- (S ) 0). In contrast, the two-electron oxidized product contains a VIII ion coupled antiferromagnetically to three ligand pi-radicals in an octahedral field[VIII(L*)3]0 (S ) 1/2).

Lowest-energy structures of (C60)nX (X=Li+,Na+,K+,Cl-) and (C60)nYCl (Y=Li,Na,K) clusters for n

PubMed

Hernández-Rojas, J; Bretón, J; Gomez Llorente, J M; Wales, D J

2004-12-22

Basin-hopping global optimization is used to find likely candidates for the lowest minima on the potential energy surface of (C(60))(n)X (X=Li(+),Na(+),K(+),Cl(-)) and (C(60))(n)YCl (Y=Li,Na,K) clusters with n

Role of the Zn1 and Zn2 sites in metallo-beta-lactamase L1.

PubMed

Hu, Zhenxin; Periyannan, Gopalraj; Bennett, Brian; Crowder, Michael W

2008-10-29

In an effort to probe the role of the Zn(II) sites in metallo-beta-lactamase L1, mononuclear metal ion containing and heterobimetallic analogues of the enzyme were generated and characterized using kinetic and spectroscopic studies. Mononuclear Zn(II)-containing L1, which binds Zn(II) in the consensus Zn1 site, was shown to be slightly active; however, this enzyme did not stabilize a nitrocefin-derived reaction intermediate that had been previously detected. Mononuclear Co(II)- and Fe(III)-containing L1 were essentially inactive, and NMR and EPR studies suggest that these metal ions bind to the consensus Zn2 site in L1. Heterobimetallic analogues (ZnCo and ZnFe) analogues of L1 were generated, and stopped-flow kinetic studies revealed that these enzymes rapidly hydrolyze nitrocefin and that there are large amounts of the reaction intermediate formed during the reaction. The heterobimetallic analogues were reacted with nitrocefin, and the reactions were rapidly freeze quenched. EPR studies on these samples demonstrate that Co(II) is 5-coordinate in the resting state, proceeds through a 4-coordinate species during the reaction, and is 5-coordinate in the enzyme-product complex. These studies demonstrate that the metal ion in the Zn1 site is essential for catalysis in L1 and that the metal ion in the Zn2 site is crucial for stabilization of the nitrocefin-derived reaction intermediate.

New biochemical insight of conserved water molecules at catalytic and structural Zn2+ ions in human matrix metalloproteinase-I: a study by MD-simulation.

PubMed

Chakrabarti, Bornali; Bairagya, Hridoy R; Mukhopadhyay, Bishnu P; Sekar, K

2017-02-01

Human matrix metalloproteinase (MMP)-1 or collagenase-1 plays a significant role in embryonic development, tissue remodeling, and is also involved in several diseases like arthritis, metastasis, etc. Molecular dynamics simulation studies on hMMP-1 X-ray structures (PDB Id. 1CGE, 1CGF, 1CGL, 1HFC, and 2TCL) suggest that the three conserved water molecules (W H/1 , W I , W S ) are coordinated with catalytic zinc (Zn C ), and one water molecule (W) is associated at structural zinc ion (Zn S ). Transition of the coordination geometry around Zn C from tetrahedral to octahedral and tetrahedral to trigonal bipyramidal at Zn S are also observed during the dynamics. Recognition of two zinc ions through water mediated bridges (Zn C - W H (W 1 )…W 2 ….H 183 - Zn S ) and stabilization of secondary coordination zone around the metal ions indicates the possibility of Zn C …Zn S coupled catalytic mechanism in hMMP-I. This study not only reveals a functionally important role of conserved water molecules in hMMP-I but also highlights the involvement of other non catalytic residues, such as S172 and D170 in the catalytic mechanism. The results obtained in this study could be relevant for importance of conserved water mediated recognition site of the sequence residue id. 202(RWTNNFREY)210, interaction of W(tryptophan)203 to zinc bound histidine, their influence on the water molecules that are involved in bridging between Zn C and Zn S , and structure-based design of specific hMMP inhibitors. Graphical abstract Water mediated recognition of structural and catalytic zinc ions of hMMP-1 structure (MD simulatated conformation).

Insight into the role of Mg2+ in hammerhead ribozyme catalysis from X-ray crystallography and molecular dynamics simulation

PubMed Central

Lee, Tai-Sung; López, Carlos Silva; Martick, Monika; Scott, William G.; York, Darrin M.

2008-01-01

Results of a series of 12 ns molecular dynamics (MD) simulations of the reactant state (with and without a Mg2+ ion), early and late transition state mimics are presented based on a recently reported crystal structure of a full-length hammerhead RNA. The simulation results support a catalytically active conformation with a Mg2+ ion bridging the A9 and scissile phosphates. In the reactant state, the Mg2+ spends significant time closely associated with the 2′OH of G8, but remains fairly distant from the leaving group O5′ position. In the early TS mimic simulation, where the nucleophilic O2′ and leaving group O5′ are equidistant from the phosphorus, the Mg2+ ion remains tightly coordinated to the 2′OH of G8, but is positioned closer to the O5′ leaving group, stabilizing the accumulating charge. In the late TS mimic simulation, the coordination around the bridging Mg2+ ion undergoes a transition whereby the coordination with the 2′OH of G8 is replace by the leaving group O5′ that has developed significant charge. At the same time, the 2′OH of G8 forms a hydrogen bond with the leaving group O5′ and is positioned to act as a general acid catalyst. This work represents the first reported simulations of the full-length hammerhead structure and TS mimics, and provides direct evidence for the possible role of a bridging Mg2+ ion in catalysis that is consistent with both crystallographic and biochemical data. PMID:19079784

Simulations of toroidal Alfvén eigenmode excited by fast ions on the Experimental Advanced Superconducting Tokamak

NASA Astrophysics Data System (ADS)

Pei, Youbin; Xiang, Nong; Shen, Wei; Hu, Youjun; Todo, Y.; Zhou, Deng; Huang, Juan

2018-05-01

Kinetic-MagnetoHydroDynamic (MHD) hybrid simulations are carried out to study fast ion driven toroidal Alfvén eigenmodes (TAEs) on the Experimental Advanced Superconducting Tokamak (EAST). The first part of this article presents the linear benchmark between two kinetic-MHD codes, namely MEGA and M3D-K, based on a realistic EAST equilibrium. Parameter scans show that the frequency and the growth rate of the TAE given by the two codes agree with each other. The second part of this article discusses the resonance interaction between the TAE and fast ions simulated by the MEGA code. The results show that the TAE exchanges energy with the co-current passing particles with the parallel velocity |v∥ | ≈VA 0/3 or |v∥ | ≈VA 0/5 , where VA 0 is the Alfvén speed on the magnetic axis. The TAE destabilized by the counter-current passing ions is also analyzed and found to have a much smaller growth rate than the co-current ions driven TAE. One of the reasons for this is found to be that the overlapping region of the TAE spatial location and the counter-current ion orbits is narrow, and thus the wave-particle energy exchange is not efficient.