Sample records for a-site cation ordering

  1. Understanding cation ordering and oxygen vacancy site preference in Ba3CaNb2O9 from first-principles

    NASA Astrophysics Data System (ADS)

    Ding, Hepeng; Virkar, Anil; Liu, Feng

    2014-03-01

    We investigate the physical mechanism underlying the formation of the B-site cation ordering and the oxygen vacancy site selection in Ba3CaNb2O9 using density functional theory calculations. We found that either cation site exchange or oxygen vacancy formation induces negligible lattice strain. This implies that the ionic radius plays an insignificant role in governing these two processes. Furthermore, the electrostatic interactions are found dominant in the ordering of mixed valence species on one or more sites, the ionic bond strength is identified as the dominant force in governing both the 1:2 B-site cation ordering along the <111>direction and the oxygen vacancy site preference in Ba3CaNb2O9. Specifically, the cation ordering can be rationalized by the increased mixing bonding energy of the Ca-O-Nb bonds over the Ca-O-Ca and Nb-O-Nb bonds, i.e., 1/2(Ca-O-Ca + Nb-O-Nb) a site to minimize the electrostatic energy and to break the weaker B-O-B bond. Funded by DOE EFRC Grant Number DE-SC0001061 as a flow through from the University of South Carolina.

  2. Intracrystalline cation order in a lunar crustal troctolite

    NASA Technical Reports Server (NTRS)

    Smyth, J. R.

    1975-01-01

    Lunar sample 76535 appears to be one of the most slowly cooled bits of silicate material yet studied. It provides, therefore, a unique opportunity for the study of ordering processes in the minerals present. A better understanding of these processes may permit better characterization of the thermal history of this and similar rocks. The cation ordering in the olivine is consistent with terrestrial olivines favoring the interpretation that ordering in olivines increases with increasing temperature. In low bronzite, the deviations from the common orthopyroxene space group appear to be caused by cation order on the basis of four M sites instead of two. The degree of cation order in each of these minerals is consistent with the rock having been excavated from its depth of formation by tectonic or impact processes without being reheated above 300 C.

  3. Discovery of the ammonium substrate site on glutamine synthetase, a third cation binding site.

    PubMed Central

    Liaw, S. H.; Kuo, I.; Eisenberg, D.

    1995-01-01

    because ADP binding induces movement of Asp 50' toward this monovalent cation site, essentially forming the site. This observation supports a two-step mechanism with ordered substrate binding: ATP first binds to GS, then Glu binds and attacks ATP to form gamma-glutamyl phosphate and ADP, which complete the ammonium binding site. The third substrate, an ammonium ion, then binds to GS, and then loses a proton to form the more active species ammonia, which attacks the gamma-glutamyl phosphate to yield Gln. (5) Because the products (Glu or Gln) of the reactions catalyzed by GS are determined by the molecule (water or ammonium) attacking the intermediate gamma-glutamyl phosphate, this negatively charged ammonium binding pocket has been designed naturally for high affinity of ammonium to GS, permitting glutamine synthesis to proceed in aqueous solution. PMID:8563633

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

    PubMed Central

    Bernuy-Lopez, Carlos; Rioja-Monllor, Laura; Nakamura, Takashi; Ricote, Sandrine; O’Hayre, Ryan; Amezawa, Koji; Einarsrud, Mari-Ann

    2018-01-01

    The effect of A-site cation ordering on the cathode performance and chemical stability of A-site cation ordered LaBaCo2O5+δ and disordered La0.5Ba0.5CoO3−δ materials are reported. Symmetric half-cells with a proton-conducting BaZr0.9Y0.1O3−δ electrolyte were prepared by ceramic processing, and good chemical compatibility of the materials was demonstrated. Both A-site ordered LaBaCo2O5+δ and A-site disordered La0.5Ba0.5CoO3−δ yield excellent cathode performance with Area Specific Resistances as low as 7.4 and 11.5 Ω·cm2 at 400 °C and 0.16 and 0.32 Ω·cm2 at 600 °C in 3% humidified synthetic air respectively. The oxygen vacancy concentration, electrical conductivity, basicity of cations and crystal structure were evaluated to rationalize the electrochemical performance of the two materials. The combination of high-basicity elements and high electrical conductivity as well as sufficient oxygen vacancy concentration explains the excellent performance of both LaBaCo2O5+δ and La0.5Ba0.5CoO3−δ materials at high temperatures. At lower temperatures, oxygen-deficiency in both materials is greatly reduced, leading to decreased performance despite the high basicity and electrical conductivity. A-site cation ordering leads to a higher oxygen vacancy concentration, which explains the better performance of LaBaCo2O5+δ. Finally, the more pronounced oxygen deficiency of the cation ordered polymorph and the lower chemical stability at reducing conditions were confirmed by coulometric titration. PMID:29373541

  5. Effect of A-Site Cation Ordering on Chemical Stability, Oxygen Stoichiometry and Electrical Conductivity in Layered LaBaCo2O5+δ Double Perovskite

    PubMed Central

    Bernuy-Lopez, Carlos; Høydalsvik, Kristin; Einarsrud, Mari-Ann; Grande, Tor

    2016-01-01

    The effect of the A-site cation ordering on the chemical stability, oxygen stoichiometry and electrical conductivity in layered LaBaCo2O5+δ double perovskite was studied as a function of temperature and partial pressure of oxygen. Tetragonal A-site cation ordered layered LaBaCo2O5+δ double perovskite was obtained by annealing cubic A-site cation disordered La0.5Ba0.5CoO3-δ perovskite at 1100 °C in N2. High temperature X-ray diffraction between room temperature (RT) and 800 °C revealed that LaBaCo2O5+δ remains tetragonal during heating in oxidizing atmosphere, but goes through two phase transitions in N2 and between 450 °C and 675 °C from tetragonal P4/mmm to orthorhombic Pmmm and back to P4/mmm due to oxygen vacancy ordering followed by disordering of the oxygen vacancies. An anisotropic chemical and thermal expansion of LaBaCo2O5+δ was demonstrated. La0.5Ba0.5CoO3-δ remained cubic at the studied temperature irrespective of partial pressure of oxygen. LaBaCo2O5+δ is metastable with respect to La0.5Ba0.5CoO3-δ at oxidizing conditions inferred from the thermal evolution of the oxygen deficiency and oxidation state of Co in the two materials. The oxidation state of Co is higher in La0.5Ba0.5CoO3-δ resulting in a higher electrical conductivity relative to LaBaCo2O5+δ. The conductivity in both materials was reduced with decreasing partial pressure of oxygen pointing to a p-type semiconducting behavior. PMID:28773279

  6. Cation ordering and effect of biaxial strain in double perovskite CsRbCaZnCl 6

    DOE PAGES

    Pilania, G.; Uberuaga, B. P.

    2015-03-19

    Here, we investigate the electronic structure, energetics of cation ordering, and effect of biaxial strain on double perovskite CsRbCaZnCl 6 using first-principles calculations based on density functional theory. The two constituents (i.e., CsCaCl 3 and RbZnCl 3) forming the double perovskite exhibit a stark contrast. While CsCaCl 3 is known to exist in a cubic perovskite structure and does not show any epitaxial strain induced phase transitions within an experimentally accessible range of compressive strains, RbZnCl 3 is thermodynamically unstable in the perovskite phase and exhibits ultra-sensitive response at small epitaxial strains if constrained in the perovskite phase. We showmore » that combining the two compositions in a double perovskite structure not only improves overall stability but also the strain-polarization coupling of the material. Our calculations predict a ground state with P4/nmm space group for the double perovskite, where A-site cations (i.e., Cs and Rb) are layer-ordered and B-site cations (i.e., Ca and Zn) prefer a rocksalt type ordering. The electronic structure and bandgap in this system are shown to be quite sensitive to the B-site cation ordering and is minimally affected by the ordering of A-site cations. We find that at experimentally accessible compressive strains CsRbCaZnCl 6 can be phase transformed from its paraelectric ground state to an antiferroelectric state, where Zn atoms contribute predominantly to the polarization. Furthermore, both energy difference and activation barrier for a transformation between this antiferroelectric state and the corresponding ferroelectric configuration are predicted to be small. As a result, the computational approach presented here opens a new pathway towards a rational design of novel double perovskites with improved strain response and functionalities.« less

  7. Topochemical synthesis of cation ordered double perovskite oxynitrides.

    PubMed

    Ceravola, Roberta; Oró-Solé, Judith; Black, Ashley P; Ritter, Clemens; Puente Orench, Inés; Mata, Ignasi; Molins, Elies; Frontera, Carlos; Fuertes, Amparo

    2017-04-19

    Topochemical nitridation in ammonia at moderate temperatures of cation ordered Sr 2 FeWO 6 produces new antiferromagnetic double perovskite oxynitrides Sr 2 FeWO 6-x N x with 0 < x ≤ 1. Nitrogen introduction induces the oxidation of Fe 2+ to Fe 3+ and decreases T N from 38 K (x = 0) to 13 K for Sr 2 FeWO 5 N which represents the first example of a double perovskite oxynitride with both high cationic order and nitrogen content. This synthetic approach can be extended to other cation combinations expanding the possibility of new materials in the large group of double perovskites.

  8. Highly conducting divalent Mg{sup 2+} cation solid electrolytes with well-ordered three-dimensional network structure

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

    Tamura, Shinji; Yamane, Megumi; Hoshino, Yasunori

    2016-03-15

    A three-dimensionally well-ordered NASICON-type Mg{sup 2+} cation conductor, (Mg{sub x}Hf{sub 1−x}){sub 4/(4−2x)}Nb(PO{sub 4}){sub 3}, was firstly developed by partial substitution of lower valent Mg{sup 2+} cation onto the Hf{sup 4+} sites in a HfNb(PO{sub 4}){sub 3} solid to realize high Mg{sup 2+} cation conductivity even at moderate temperatures. Due to the formation of well-ordered NASICON-type structure, both the high Mg{sup 2+} cation conductivity below 450 °C and the low activation energy for Mg{sup 2+} cation migration was successfully realized for the (Mg{sub 0.1}Hf{sub 0.9}){sub 4/3.8}Nb(PO{sub 4}){sub 3} solid. Pure Mg{sup 2+} cation conduction in the NASICON-type (Mg{sub 0.1}Hf{sub 0.9}){sub 4/3.8}Nb(PO{submore » 4}){sub 3} solid was directly and quantitatively demonstrated by means of two kinds of dc electrolysis. - Graphical abstract: Image of the Mg{sup 2+} cation conduction in NASICON-type (Mg{sub 0.1}Hf{sub 0.9}){sub 4/3.8}Nb(PO{sub 4}){sub 3} and its Mg{sup 2+} conductivity. - Highlights: • We develop a three-dimensionally well-ordered NASICON-type Mg{sup 2+} cation conductor. • A high magnesium cation conductivity is realized even at moderate temperatures. • Divalent magnesium cation conduction is demonstrated directly and quantitatively.« less

  9. Titanomagnetite Curie temperatures: Effects of vacancies, chemical/cation ordering and thermal history

    NASA Astrophysics Data System (ADS)

    Jackson, M. J.; Bowles, J. A.; Lappe, S. C. L. L.; Solheid, P.

    2016-12-01

    Recent experimental work [Bowles et al, 2013, Nat. Commun.; Jackson and Bowles, 2014, G-cubed] has shown that the Curie temperatures (Tc) of intermediate-composition titanomagnetites (TM30-TM50) depend strongly on thermal history, with Tc increases of ≥100°C produced by moderate-temperature (300°-400° C) annealing in the lab or in slow natural cooling. Equally large decreases are produced by rapid cooling ("quenching") from higher temperatures. The phenomenon is robustly defined and repeatable, but the underlying mechanism remains enigmatic, presumably involving rearrangement of metal cations within the spinel lattice without any change in bulk composition. Previous studies [e.g., Moskowitz and Wanamaker, 1994, GRL; Lattard et al, 2006, JGR] have shown that cation deficiency controls Tc both directly, by changing the ferrous/ferric ratio, and indirectly, by affecting the cation ordering. Our new experiments examined the effects of oxidation state and nonstoichiometry on the magnitude of Tc changes produced by quenching/annealing. In our synthetic TMs these changes are generally relatively small (ΔTc<35°), but when the samples are oxidized by heating in air (150°-250°C for 23-110 h) prior to annealing (300°-400° C for 10-1000 h in vacuum), ΔTc reaches 100°C or more, similar to the changes observed in our natural TMs. Conversely, in our natural samples annealing and quenching can cause quite large changes (ΔTc>100°), but when the samples are embedded in a reducing material (containing graphite), ΔTc becomes insignificant. These results strongly suggest that cation vacancies play an essential role in the cation rearrangements responsible for the observed changes in Tc. XMCD and low-temperature Mossbauer and magnetization measurements show no evidence of corresponding changes in ferrous/ferric site occupancy, and some form of octahedral-site chemical clustering or short-range ordering appears to be the best way to explain the large observed changes in

  10. Active-site monovalent cations revealed in a 1.55-Å-resolution hammerhead ribozyme structure.

    PubMed

    Anderson, Michael; Schultz, Eric P; Martick, Monika; Scott, William G

    2013-10-23

    We have obtained a 1.55-Å crystal structure of a hammerhead ribozyme derived from Schistosoma mansoni under conditions that permit detailed observations of Na(+) ion binding in the ribozyme's active site. At least two such Na(+) ions are observed. The first Na(+) ion binds to the N7 of G10.1 and the adjacent A9 phosphate in a manner identical with that previously observed for divalent cations. A second Na(+) ion binds to the Hoogsteen face of G12, the general base in the hammerhead cleavage reaction, thereby potentially dissipating the negative charge of the catalytically active enolate form of the nucleotide base. A potential but more ambiguous third site bridges the A9 and scissile phosphates in a manner consistent with that of previous predictions. Hammerhead ribozymes have been observed to be active in the presence of high concentrations of monovalent cations, including Na(+), but the mechanism by which monovalent cations substitute for divalent cations in hammerhead catalysis remains unclear. Our results enable us to suggest that Na(+) directly and specifically substitutes for divalent cations in the hammerhead active site. The detailed geometry of the pre-catalytic active-site complex is also revealed with a new level of precision, thanks to the quality of the electron density maps obtained from what is currently the highest-resolution ribozyme structure in the Protein Data Bank. Copyright © 2013 Elsevier Ltd. All rights reserved.

  11. High-pressure synthesis, crystal chemistry and physics of perovskites with small cations at the A site.

    PubMed

    Belik, Alexei A; Yi, Wei

    2014-04-23

    ABO3 perovskites with small cations at the A site (A = Sc(3+), In(3+) and Mn(2+) and B = Al(3+) and transition metals) are reviewed. They extend the corresponding families of perovskites with A(3+) = Y, La-Lu, and Bi and A(2+) = Cd, Ca, Sr and Ba and exhibit the largest structural distortions. As a result of these large distortions, they show, in many cases, distinct structural and magnetic properties. These are manifested in: B-site-ordered monoclinic structures of ScMnO3 and 'InMnO3'; an unusual superstructure of ScRhO3 and InRhO3; antiferromagnetic ground states and multiferroic properties of Sc2NiMnO6 and In2NiMnO6; two magnetic transitions in ScCrO3 and InCrO3 with very close transition temperatures; a Pnma-to-P-1 structural transition and k = (½, 0, ½) magnetic ordering in ScVO3; and incommensurate magnetic ordering of Mn(2+) spins in metallic MnVO3. A large number of simple ScBO3, InBO3 and MnBO3 perovskites has not been synthesized yet, and the number of experimental and theoretical works on each known ScBO3, InBO3 and MnBO3 perovskites counts to only one or two (except for ScAlO3). The synthesis, crystal chemistry and physics of perovskites with small cations at the A site is an emerging field in perovskite science.

  12. A cation-pi interaction in the binding site of the glycine receptor is mediated by a phenylalanine residue.

    PubMed

    Pless, Stephan A; Millen, Kat S; Hanek, Ariele P; Lynch, Joseph W; Lester, Henry A; Lummis, Sarah C R; Dougherty, Dennis A

    2008-10-22

    Cys-loop receptor binding sites characteristically contain many aromatic amino acids. In nicotinic ACh and 5-HT3 receptors, a Trp residue forms a cation-pi interaction with the agonist, whereas in GABA(A) receptors, a Tyr performs this role. The glycine receptor binding site, however, contains predominantly Phe residues. Homology models suggest that two of these Phe side chains, Phe159 and Phe207, and possibly a third, Phe63, are positioned such that they could contribute to a cation-pi interaction with the primary amine of glycine. Here, we test this hypothesis by incorporation of a series of fluorinated Phe derivatives using unnatural amino acid mutagenesis. The data reveal a clear correlation between the glycine EC(50) value and the cation-pi binding ability of the fluorinated Phe derivatives at position 159, but not at positions 207 or 63, indicating a single cation-pi interaction between glycine and Phe159. The data thus provide an anchor point for locating glycine in its binding site, and demonstrate for the first time a cation-pi interaction between Phe and a neurotransmitter.

  13. Regulation by divalent cations of /sup 3/H-baclofen binding to GABA/sub B/ sites in rat cerebellar membranes

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

    Kato, K.; Goto, M.; Fukuda, H.

    1983-02-21

    When investigating the effects of divalent cations (Mg/sup 2 +/, Ca/sup 2 +/, Sr/sup 2 +/, Ba/sup 2 +/, Mn/sup 2 +/ and Ni/sup 2 +/) on /sup 3/H-baclofen binding to rat cerebellar synaptic membranes, we found that the specific binding of /sup 3/H-baclofen was not only dependent on divalent cations, but was increased dose-dependently in the presence of these cations. The effects were in the following order of potency: Mn/sup 2 +/ approx. = Ni/sup 2 +/ > Mg/sup 2 +/ > Ca/sup 2 +/ > Sr/sup 2 +/ > Ba/sup 2 +/. Scatchard analysis of the binding datamore » revealed a single component of the binding sites in the presence of 2.5 mM MgCl/sub 2/, 2.5 mM CaCl/sub 2/ or 0.3 mM MnCl/sub 2/ whereas two components appeared in the presence of 2.5 mM MnCl/sub 2/ or 1 mM NiCl/sub 2/. In the former, divalent cations altered the apparent affinity (K/sub d/) without affecting density of the binding sites (B/sub max/). In the latter, the high-affinity sites showed a higher affinity and lower density of the binding sites than did the single component of the former. As the maximal effects of four cations (Mg/sup 2 +/, Ca/sup 2 +/, Mn/sup 2 +/, and Ni/sup 2 +/) were not additive, there are probably common sites of action of these divalent cations. Among the ligands for GABA/sub B/ sites, the affinity for (-), (+) and (+/-)baclofen, GABA and ..beta..-phenyl GABA increased 2 - 6 fold in the presence of 2.5 mM MnCl/sub 2/, in comparison with that in HEPES-buffered Krebs solution (containing 2.5 mM CaCl/sub 2/ and 1.2 mM MgSO/sub 4/), whereas that for muscimol was decreased to one-fifth. Thus, the affinity of GABA/sub B/ sites for its ligands is probably regulated by divalent cations, through common sites of action.« less

  14. XMCD and XAS examination of cation ordering in synthetic Mg- and Al-substituted titanomagnetites

    NASA Astrophysics Data System (ADS)

    Lappe, S. C. L. L.; Bowles, J.; Jackson, M.; Arenholz, E.

    2015-12-01

    composition. X-ray absorption spectra (XAS) of the Ti, Mg and Al show no significant differences for samples of different anneal stages, suggesting no reordering of the Ti4+, Al3+ and Mg2+. The lack of observed (re)ordering between A and B lattice sites suggests the process may be vacancy mediated or there might be short-range cation (re)ordering within the lattice sites.

  15. Structure and cation ordering in La 2UO 6, Ce 2UO 6, LaUO 4, and CeUO 4 by first principles calculations

    DOE PAGES

    Casillas-Trujillo, Luis; Xu, H.; McMurray, Jake W.; ...

    2016-07-06

    In the present work, we have used density functional theory (DFT) and DFT+U to investigate the crystal structure and phase stability of four model compounds in the Ln 2O 3-UO 2-UO 3 ternary oxide system: La2UO 6, Ce 2UO 6, LaUO 4, CeUO 4, due to the highly-correlated nature of the f-electrons in uranium. We have considered both hypothetical ordered compounds and compounds in which the cations randomly occupy atomic sites in a fluorite-like lattice. We determined that ordered compounds are stable and are energetically favored compared to disordered configurations, though the ordering tendencies are weak. To model and analyzemore » the structures of these complex oxides, we have used supercells based on a layered atomic model. In the layer model, the supercell is composed of alternating planes of anions and cations. We have considered two different ordering motifs for the cations, namely single species (isoatomic) cation layers versus mixed species cation layers. Energy differences between various ordered cationic arrangements were found to be small. This may have implications regarding radiation stability, since cationic arrangements should be able to change under irradiation with little cost in energy.« less

  16. Effect of cation ordering on oxygen vacancy diffusion pathways in double perovskites

    DOE PAGES

    Uberuaga, Blas Pedro; Pilania, Ghanshyam

    2015-07-08

    Perovskite structured oxides (ABO 3) are attractive for a number of technological applications, including as superionics because of the high oxygen conductivities they exhibit. Double perovskites (AA’BB’O 6) provide even more flexibility for tailoring properties. Using accelerated molecular dynamics, we examine the role of cation ordering on oxygen vacancy mobility in one model double perovskite SrLaTiAlO 6. We find that the mobility of the vacancy is very sensitive to the cation ordering, with a migration energy that varies from 0.6 to 2.7 eV. In the extreme cases, the mobility is both higher and lower than either of the two endmore » member single perovskites. Further, the nature of oxygen vacancy diffusion, whether one-dimensional, two-dimensional, or three-dimensional, also varies with cation ordering. We correlate the dependence of oxygen mobility on cation structure to the distribution of Ti 4+ cations, which provide unfavorable environments for the positively charged oxygen vacancy. The results demonstrate the potential of using tailored double perovskite structures to precisely control the behavior of oxygen vacancies in these materials.« less

  17. High stability of electro-transport and magnetism against the A-site cation disorder in SrRuO3

    PubMed Central

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

    2016-01-01

    It is known that the electro-transport and magnetism of perovskite alkaline-earth ruthenate oxides are sensitive to the lattice distortion associated with the A-site cation size. Orthorhombic CaRuO3 and cubic BaRuO3 exhibit distinctly different electro-transport and magnetic properties from orthorhombic SrRuO3. It has been suggested that SrRuO3 can be robust against some intrinsic/external perturbations but fragile against some others in terms of electro-transport and magnetism, and it is our motivation to explore such stability against the local site cation disorder. In this work, we prepare a set of SrRuO3-based samples with identical averaged A-site size but different A-site cation disorder (size mismatch) by Ca and Ba co-substitution of Sr. It is revealed that the electro-transport and magnetism of SrRuO3 demonstrate relatively high stability against this A-site cation disorder, characterized by the relatively invariable electrical and magnetic properties in comparison with those of SrRuO3 itself. A simple electro-transport network model is proposed to explain quantitatively the measured behaviors. The present work suggests that SrRuO3 as an itinerant electron ferromagnetic metal possesses relatively high robustness against local lattice distortion and cation occupation disorder. PMID:27297396

  18. Scandium induced structural transformation and B′:B″ cationic ordering in Pb(Fe{sub 0.5}Nb{sub 0.5})O{sub 3} multiferroic ceramics

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

    Mallesham, B.; Ranjith, R., E-mail: ranjith@iith.ac.in; Manivelraja, M.

    2014-07-21

    The current study explores non-magnetic Sc{sup 3+} induced structural transformation, evolution of local B-site cation ordering and associated effect on ferroelectric phase transition temperature T{sub max} (temperature corresponding to dielectric maxima) on increasing the atom percent of Sc substitution in [Pb(Fe{sub 0.5}Nb{sub 0.5})O{sub 3} (PFN)] ceramics. In this regard, the phase pure Pb[(Fe{sub 0.5−x}Sc{sub x})Nb{sub 0.5}]O{sub 3} ceramics with x varying from 0 to 0.5 were synthesized through solid state reaction route. The detailed structural analysis through Rietveld refinement confirms the room temperature transformation from a monoclinic Cm to rhombohedral R3m structure at x = 0.3 mol. % of Sc. Absorption spectra studies showmore » that there is a considerable increment in the bandgap at higher scandium content. Most interestingly, the T{sub max} exhibited an increment for lower scandium contents (x = 0.1 to 0.25) followed by a drop in T{sub max} (x = 0.3 to 0.5). Such anomalous behavior in T{sub max} is expected to arise due to the onset of B′, B″ local cation ordering beyond Sc content x = 0.25. The B-site cation ordering at and beyond x = 0.3 was also confirmed by the evolution of cation order induced Pb-O coupled vibrational mode in Raman scattering studies. In addition, the Mössbauer spectra of PFN (x = 0) and Pb(Fe{sub 0.4}Sc{sub 0.1}Nb{sub 0.5})O{sub 3} (x = 0.1) are reported to verify the spin state and oxidation state of iron. The lattice distortion due to the radius ratio difference between a Sc{sup 3+} cation and Fe{sup 3+} cation in low spin state is responsible for the structural transformation, which in turn facilitates a B′:B″ cation ordering.« less

  19. Atomic-scale analysis of cation ordering in reduced calcium titanate.

    PubMed

    Li, Luying; Hu, Xiaokang; Jiang, Fan; Jing, Wenkui; Guo, Cong; Jia, Shuangfeng; Gao, Yihua; Wang, Jianbo

    2017-11-03

    The phenomenon of cation ordering is closely related to certain physical properties of complex oxides, which necessitates the search of underlying structure-property relationship at atomic resolution. Here we study the superlattices within reduced calcium titanate single crystal micro-pillars, which are unexpected from the originally proposed atomic model. Bright and dark contrasts at alternating Ti double layers perpendicular to b axis are clearly observed, but show no signs in corresponding image simulations based on the proposed atomic model. The multi-dimensional chemical analyses at atomic resolution reveal periodic lower Ti concentrations at alternating Ti double layers perpendicular to b axis. The following in-situ heating experiment shows no phase transition at the reported T c and temperature independence of the superlattices. The dimerization of the Ti-Ti bonds at neighboring double rutile-type chains within Ti puckered sheets are directly observed, which is found to be not disturbed by the cation ordering at alternating Ti double layers. The characterization of cation ordering of complex oxides from chemical and structural point of view at atomic resolution, and its reaction to temperature variations are important for further understanding their basic physical properties and exploiting potential applications.

  20. Probing cation and vacancy ordering in the dry and hydrated yttrium-substituted BaSnO3 perovskite by NMR spectroscopy and first principles calculations: implications for proton mobility.

    PubMed

    Buannic, Lucienne; Blanc, Frédéric; Middlemiss, Derek S; Grey, Clare P

    2012-09-05

    Hydrated BaSn(1-x)Y(x)O(3-x/2) is a protonic conductor that, unlike many other related perovskites, shows high conductivity even at high substitution levels. A joint multinuclear NMR spectroscopy and density functional theory (total energy and GIPAW NMR calculations) investigation of BaSn(1-x)Y(x)O(3-x/2) (0.10 ≤ x ≤ 0.50) was performed to investigate cation ordering and the location of the oxygen vacancies in the dry material. The DFT energetics show that Y doping on the Sn site is favored over doping on the Ba site. The (119)Sn chemical shifts are sensitive to the number of neighboring Sn and Y cations, an experimental observation that is supported by the GIPAW calculations and that allows clustering to be monitored: Y substitution on the Sn sublattice is close to random up to x = 0.20, while at higher substitution levels, Y-O-Y linkages are avoided, leading, at x = 0.50, to strict Y-O-Sn alternation of B-site cations. These results are confirmed by the absence of a "Y-O-Y" (17)O resonance and supported by the (17)O NMR shift calculations. Although resonances due to six-coordinate Y cations were observed by (89)Y NMR, the agreement between the experimental and calculated shifts was poor. Five-coordinate Sn and Y sites (i.e., sites next to the vacancy) were observed by (119)Sn and (89)Y NMR, respectively, these sites disappearing on hydration. More five-coordinated Sn than five-coordinated Y sites are seen, even at x = 0.50, which is ascribed to the presence of residual Sn-O-Sn defects in the cation-ordered material and their ability to accommodate O vacancies. High-temperature (119)Sn NMR reveals that the O ions are mobile above 400 °C, oxygen mobility being required to hydrate these materials. The high protonic mobility, even in the high Y-content materials, is ascribed to the Y-O-Sn cation ordering, which prevents proton trapping on the more basic Y-O-Y sites.

  1. Selectivity of externally facing ion-binding sites in the Na/K pump to alkali metals and organic cations

    PubMed Central

    Ratheal, Ian M.; Virgin, Gail K.; Yu, Haibo; Roux, Benoît; Gatto, Craig; Artigas, Pablo

    2010-01-01

    The Na/K pump is a P-type ATPase that exchanges three intracellular Na+ ions for two extracellular K+ ions through the plasmalemma of nearly all animal cells. The mechanisms involved in cation selection by the pump's ion-binding sites (site I and site II bind either Na+ or K+; site III binds only Na+) are poorly understood. We studied cation selectivity by outward-facing sites (high K+ affinity) of Na/K pumps expressed in Xenopus oocytes, under voltage clamp. Guanidinium+, methylguanidinium+, and aminoguanidinium+ produced two phenomena possibly reflecting actions at site III: (i) voltage-dependent inhibition (VDI) of outwardly directed pump current at saturating K+, and (ii) induction of pump-mediated, guanidinium-derivative–carried inward current at negative potentials without Na+ and K+. In contrast, formamidinium+ and acetamidinium+ induced K+-like outward currents. Measurement of ouabain-sensitive ATPase activity and radiolabeled cation uptake confirmed that these cations are external K+ congeners. Molecular dynamics simulations indicate that bound organic cations induce minor distortion of the binding sites. Among tested metals, only Li+ induced Na+-like VDI, whereas all metals tested except Na+ induced K+-like outward currents. Pump-mediated K+-like organic cation transport challenges the concept of rigid structural models in which ion specificity at site I and site II arises from a precise and unique arrangement of coordinating ligands. Furthermore, actions by guanidinium+ derivatives suggest that Na+ binds to site III in a hydrated form and that the inward current observed without external Na+ and K+ represents cation transport when normal occlusion at sites I and II is impaired. These results provide insights on external ion selectivity at the three binding sites. PMID:20937860

  2. B-Site Metal Cation Exchange in Halide Perovskites

    DOE PAGES

    Eperon, Giles E.; Ginger, David S.

    2017-05-02

    Here, we demonstrate exchange of the B-site metal cation in hybrid organic-inorganic halide perovskite thin films. We exchange tin in formamidinium tin triiodide (NH 2) 2SnI 3' or FASnI 3) with lead at controllable levels, forming (CH- (NH 2) 2SnI xPB 1-xI 3 alloys with partial substitution and fully converting the film to CH(NH 2) 2PbI 3 with a large excess of Pb 2+. We observe no evidence for phase segregation or bilayered films, indicating that conversion is uniform throughout the film. This facile technique provides a new way to control composition independently from the crystallization processes, allowing formation ofmore » the black phase of CH(NH 2) 2PbI 3 at much lower temperatures than those previously reported while also opening the door to new morphology-composition combinations. The surprising observation that the B-site metal cations are mobile may also provide insight into the nature of transient processes in these materials, suggesting that they may be involved in ionic conduction, and will be a critical consideration for long-term stability.« less

  3. B-Site Metal Cation Exchange in Halide Perovskites

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

    Eperon, Giles E.; Ginger, David S.

    Here, we demonstrate exchange of the B-site metal cation in hybrid organic-inorganic halide perovskite thin films. We exchange tin in formamidinium tin triiodide (NH 2) 2SnI 3' or FASnI 3) with lead at controllable levels, forming (CH- (NH 2) 2SnI xPB 1-xI 3 alloys with partial substitution and fully converting the film to CH(NH 2) 2PbI 3 with a large excess of Pb 2+. We observe no evidence for phase segregation or bilayered films, indicating that conversion is uniform throughout the film. This facile technique provides a new way to control composition independently from the crystallization processes, allowing formation ofmore » the black phase of CH(NH 2) 2PbI 3 at much lower temperatures than those previously reported while also opening the door to new morphology-composition combinations. The surprising observation that the B-site metal cations are mobile may also provide insight into the nature of transient processes in these materials, suggesting that they may be involved in ionic conduction, and will be a critical consideration for long-term stability.« less

  4. Investigation of Local Structures in Cation-ordered Microwave Dielectric A Solid-state NMR and First Principle Calculation Study

    NASA Astrophysics Data System (ADS)

    Kalfarisi, Rony G.

    Solid-state Nuclear Magnetic Resonance (ssNMR) spectroscopy has proven to be a powerful method to probe the local structure and dynamics of a system. In powdered solids, the nuclear spins experience various anisotropic interactions which depend on the molecular orientation. These anisotropic interactions make ssNMR very useful as they give a specific appearance to the resonance lines of the spectra. The position and shape of these resonance lines can be related to local structure and dynamics of the system under study. My research interest has focused around studying local structures and dynamics of quadrupolar nuclei in materials using ssNMR spectroscopy. 7Li and 93Nb ssNMR magic angle spinning (MAS) spectra, acquired at 17.6 and 7.06 T, have been used to evaluate the structural and dynamical properties of cation-ordered microwave dielectric materials. Microwave dielectric materials are essential in the application of wireless telecommunication, biomedical engineering, and other scientific and industrial implementations that use radio and microwave signals. The study of the local environment with respect to average structure, such as X-ray diffraction study, is essential for the better understanding of the correlations between structures and properties of these materials. The investigation for short and medium range can be performed with the use of ssNMR techniques. Even though XRD results show cationic ordering at the B-site (third coordination sphere), NMR spectra show a presence of disorder materials. This was indicated by the observation of a distribution in NMR parameters derived from experimental . {93}Nb NMR spectraand supported by theoretical calculations.

  5. Zhang-Rice physics and anomalous copper states in A-site ordered perovskites

    PubMed Central

    Meyers, D.; Mukherjee, Swarnakamal; Cheng, J.-G.; Middey, S.; Zhou, J.-S.; Goodenough, J. B.; Gray, B. A.; Freeland, J. W.; Saha-Dasgupta, T.; Chakhalian, J.

    2013-01-01

    In low dimensional cuprates several interesting phenomena, including high Tc superconductivity, are deeply connected to electron correlations on Cu and the presence of the Zhang-Rice (ZR) singlet state. Here, we report on direct spectroscopic observation of the ZR state responsible for the low-energy physical properties in two isostructural A-site ordered cuprate perovskites, CaCu3Co4O12 and CaCu3Cr4O12 as revealed by resonant soft x-ray absorption spectroscopy on the Cu L3,2- and O K-edges. These measurements reveal the signature of Cu in the high-energy 3+ (3d8), the typical 2+ (3d9), as well as features of the ZR singlet state (i.e., 3d9L, L denotes an oxygen hole). First principles GGA + U calculations affirm that the B-site cation controls the degree of Cu-O hybridization and, thus, the Cu valency. These findings introduce another avenue for the study and manipulation of cuprates, bypassing the complexities inherent to conventional chemical doping (i.e. disorder) that hinder the relevant physics. PMID:23666066

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

    NASA Astrophysics Data System (ADS)

    Wolverton, C.; Zunger, Alex

    1998-03-01

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

  7. First-principles theory of cation and intercalation ordering in Li xCoO 2

    NASA Astrophysics Data System (ADS)

    Wolverton, C.; Zunger, Alex

    Several types of cation- and vacancy-ordering are of interest in the Li xCoO 2 battery cathode material since they can have a profound effect on the battery voltage. We present a first-principles theoretical approach which can be used to calculate both cation- and vacancy-ordering patterns at both zero and finite temperatures. This theory also provides quantum-mechanical predictions (i.e., without the use of any experimental input) of battery voltages of both ordered and disordered Li xCoO 2/Li cells from the energetics of the Li intercalation reactions. Our calculations allow us to search the entire configurational space to predict the lowest-energy ground-state structures, search for large voltage cathodes, explore metastable low-energy states, and extend our calculations to finite temperatures, thereby searching for order-disorder transitions and states of partial disorder. We present the first prediction of the stable spinel structure LiCo 2O 4 for the 50% delithiated Li 0.5CoO 2.

  8. Kinetics of Cation and Oxyanion Adsorption and Desorption on Ferrihydrite: Roles of Ferrihydrite Binding Sites and a Unified Model.

    PubMed

    Tian, Lei; Shi, Zhenqing; Lu, Yang; Dohnalkova, Alice C; Lin, Zhang; Dang, Zhi

    2017-09-19

    Quantitative understanding the kinetics of toxic ion reactions with various heterogeneous ferrihydrite binding sites is crucial for accurately predicting the dynamic behavior of contaminants in environment. In this study, kinetics of As(V), Cr(VI), Cu(II), and Pb(II) adsorption and desorption on ferrihydrite was studied using a stirred-flow method, which showed that metal adsorption/desorption kinetics was highly dependent on the reaction conditions and varied significantly among four metals. High resolution scanning transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy showed that all four metals were distributed within the ferrihydrite aggregates homogeneously after adsorption reactions. Based on the equilibrium model CD-MUSIC, we developed a novel unified kinetics model applicable for both cation and oxyanion adsorption and desorption on ferrihydrite, which is able to account for the heterogeneity of ferrihydrite binding sites, different binding properties of cations and oxyanions, and variations of solution chemistry. The model described the kinetic results well. We quantitatively elucidated how the equilibrium properties of the cation and oxyanion binding to various ferrihydrite sites and the formation of various surface complexes controlled the adsorption and desorption kinetics at different reaction conditions and time scales. Our study provided a unified modeling method for the kinetics of ion adsorption/desorption on ferrihydrite.

  9. Cation disorder in Ga1212.

    PubMed

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

    2000-07-24

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

  10. Examination of the effect of the annealing cation on higher order structures containing guanine or isoguanine repeats

    PubMed Central

    Pierce, Sarah E.; Wang, Junmei; Jayawickramarajah, Janarthanan; Hamilton, Andrew D.; Brodbelt, Jennifer S.

    2010-01-01

    Isoguanine (2-oxo-6-amino-guanine), a natural but non-standard base, exhibits unique self-association properties compared to its isomer, guanine, and results in formation of different higher order DNA structures. In this work, the higher order structures formed by oligonucleotides containing guanine repeats or isoguanine repeats after annealing in solutions containing various cations are evaluated by electrospray ionization mass spectrometry (ESI-MS) and circular dichroism (CD) spectroscopy. The guanine-containing strand (G9) consistently formed quadruplexes upon annealing, whereas the isoguanine strand (Ig9) formed both pentaplexes and quadruplexes depending on the annealing cation. Quadruplex formation with G9 showed some dependence on the identity of the cation present during annealing with high relative quadruplex formation detected with six of ten cations. Analogous annealing experiments with Ig9 resulted in complex formation with all ten cations, and the majority of the resulting complexes were pentaplexes. CD results indicated most of the original complexes survived the desalting process necessary for ESI-MS analysis. In addition, several complexes, especially the pentaplexes, were found to be capable of cation exchange with ammonium ions. Ab initio calculations were conducted for isoguanine tetrads and pentads coordinated with all ten cations to predict the most energetically stable structures of the complexes in the gas phase. The observed preference of forming quadruplexes versus pentaplexes as a function of the coordinated cation can be interpreted by the calculated reaction energies of both the tetrads and pentads in combination with the distortion energies of tetrads. PMID:19746468

  11. Identification of cation-binding sites on actin that drive polymerization and modulate bending stiffness

    PubMed Central

    Kang, Hyeran; Bradley, Michael J.; McCullough, Brannon R.; Pierre, Anaëlle; Grintsevich, Elena E.; Reisler, Emil; De La Cruz, Enrique M.

    2012-01-01

    The assembly of actin monomers into filaments and networks plays vital roles throughout eukaryotic biology, including intracellular transport, cell motility, cell division, determining cellular shape, and providing cells with mechanical strength. The regulation of actin assembly and modulation of filament mechanical properties are critical for proper actin function. It is well established that physiological salt concentrations promote actin assembly and alter the overall bending mechanics of assembled filaments and networks. However, the molecular origins of these salt-dependent effects, particularly if they involve nonspecific ionic strength effects or specific ion-binding interactions, are unknown. Here, we demonstrate that specific cation binding at two discrete sites situated between adjacent subunits along the long-pitch helix drive actin polymerization and determine the filament bending rigidity. We classify the two sites as “polymerization” and “stiffness” sites based on the effects that mutations at the sites have on salt-dependent filament assembly and bending mechanics, respectively. These results establish the existence and location of the cation-binding sites that confer salt dependence to the assembly and mechanics of actin filaments. PMID:23027950

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

    NASA Astrophysics Data System (ADS)

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

    2000-07-01

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

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

    PubMed

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

    2016-05-28

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

  14. Tuning the ion selectivity of tetrameric cation channels by changing the number of ion binding sites

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

    Derebe, Mehabaw G.; Sauer, David B.; Zeng, Weizhong

    2015-11-30

    Selective ion conduction across ion channel pores is central to cellular physiology. To understand the underlying principles of ion selectivity in tetrameric cation channels, we engineered a set of cation channel pores based on the nonselective NaK channel and determined their structures to high resolution. These structures showcase an ensemble of selectivity filters with a various number of contiguous ion binding sites ranging from 2 to 4, with each individual site maintaining a geometry and ligand environment virtually identical to that of equivalent sites in K{sup +} channel selectivity filters. Combined with single channel electrophysiology, we show that only themore » channel with four ion binding sites is K{sup +} selective, whereas those with two or three are nonselective and permeate Na{sup +} and K{sup +} equally well. These observations strongly suggest that the number of contiguous ion binding sites in a single file is the key determinant of the channel's selectivity properties and the presence of four sites in K{sup +} channels is essential for highly selective and efficient permeation of K{sup +} ions.« less

  15. Ordered microporous layered lanthanide 1,3,5-benzenetriphosphonates pillared with cationic organic molecules.

    PubMed

    Araki, Takahiro; Kondo, Atsushi; Maeda, Kazuyuki

    2015-04-13

    Novel isomorphous pillared-layer-type crystalline lanthanide 1,3,5-benzenetriphosphonates were prepared with bpy and dbo as organic pillars (LnBP-bpy and LnBP-dbo; Ln: Ce, Pr, and Nd). Ab initio crystal structure solution using synchrotron X-ray powder diffraction data revealed that the organic pillars do not exist as neutral coordinating ligands but as cationic molecules. Especially the LnBP-dbo phases have ordered interlayer space filled with water molecules between the dbo pillars, and the interlayer water is successfully removed by heating under vacuum with slightly distorted but basically retained pillared layer structures. Microporosity of the materials is confirmed by adsorption of nitrogen, carbon dioxide, and hydrogen gases. Such microporous layered metal phosphonates pillared with cationic molecules should be unprecedented and should offer new strategies to design ordered microporous materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Cations in Octahedral Sites: A Descriptor for Oxygen Electrocatalysis on Transition-Metal Spinels

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

    Wei, Chao; Feng, Zhenxing; Scherer, Günther G.

    2017-04-10

    Exploring efficient and low-cost electrocatalysts for the oxygen-reduction reaction (ORR) and oxygen-evolution reaction (OER) is critical for developing renewable energy technologies such as fuel cells, metal–air batteries, and water electrolyzers. A rational design of a catalyst can be guided by identifying descriptors that determine its activity. Here, a descriptor study on the ORR/OER of spinel oxides is presented. With a series of MnCo2O4, the Mn in octahedral sites is identified as an active site. This finding is then applied to successfully explain the ORR/OER activities of other transition-metal spinels, including MnxCo3-xO4 (x = 2, 2.5, 3), LixMn2O4 (x = 0.7,more » 1), XCo2O4 (X = Co, Ni, Zn), and XFe2O4 (X = Mn, Co, Ni). A general principle is concluded that the eg occupancy of the active cation in the octahedral site is the activity descriptor for the ORR/OER of spinels, consolidating the role of electron orbital filling in metal oxide catalysis.« less

  17. Cation binding at the node of Ranvier: I. Localization of binding sites during development.

    PubMed

    Zagoren, J C; Raine, C S; Suzuki, K

    1982-06-17

    Cations are known to bind to the node of Ranvier and the paranodal regions of myelinated fibers. The integrity of these specialized structures is essential for normal conduction. Sites of cation binding can be microscopically identified by the electrondense histochemical reaction product formed by the precipitate of copper sulfate/potassium ferrocyanide. This technique was used to study the distribution of cation binding during normal development of myelinating fibers. Sciatic nerves of C57B1 mice, at 1, 3, 5, 6, 7, 8, 9, 13, 16, 18, 24 and 30 days of age, were prepared for electron microscopy following fixation in phosphate-buffered 2.5% glutaraldehyde and 1% osmic acid, microdissection and incubation in phosphate-buffered 0.1 M cupric sulfate followed by 0.1 M potassium ferrocyanide. Localization of reaction product was studied by light and electron microscopy. By light microscopy, no reaction product was observed prior to 9 days of age. At 13 days, a few nodes and paranodes exhibited reaction product. This increased in frequency and intensity up to 30 days when almost all nodes or paranodes exhibited reaction product. Ultrastructurally, diffuse reaction product was first observed at 3 days of age in the axoplasm of the node, in the paranodal extracellular space of the terminal loops, in the Schwann cell proper and in the terminal loops of Schwann cell cytoplasm. When myelinated axons fulfilled the criteria for mature nodes, reaction product was no longer observed in the Schwann cell cytoplasm, while the intensity of reaction product in the nodal axoplasm and paranodal extracellular space of the terminal loops increased. Reaction product in the latter site appeared to be interrupted by the transverse bands. These results suggest that cation binding accompanies nodal maturity and that the Schwann cell may play a role in production or storage of the cation binding substance during myelinogenesis and development.

  18. A-site ordered quadruple perovskite oxides

    NASA Astrophysics Data System (ADS)

    Youwen, Long

    2016-07-01

    The A-site ordered perovskite oxides with chemical formula display many intriguing physical properties due to the introduction of transition metals at both A‧ and B sites. Here, research on the recently discovered intermetallic charge transfer occurring between A‧-site Cu and B-site Fe ions in LaCu3Fe4O12 and its analogues is reviewed, along with work on the magnetoelectric multiferroicity observed in LaMn3Cr4O12 with cubic perovskite structure. The Cu-Fe intermetallic charge transfer leads to a first-order isostructural phase transition accompanied by drastic variations in magnetism and electrical transport properties. The LaMn3Cr4O12 is a novel spin-driven multiferroic system with strong magnetoelectric coupling effects. The compound is the first example of cubic perovskite multiferroics to be found. It opens up a new arena for studying unexpected multiferroic mechanisms. Project supported by the National Basic Research Program of China (Grant No. 2014CB921500), the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant No. XDB07030300), and the National Natural Science Foundation of China (Grant No. 11574378).

  19. Interactions of divalent cations with calcium binding sites of BK channels reveal independent motions within the gating ring.

    PubMed

    Miranda, Pablo; Giraldez, Teresa; Holmgren, Miguel

    2016-12-06

    Large-conductance voltage- and calcium-activated K + (BK) channels are key physiological players in muscle, nerve, and endocrine function by integrating intracellular Ca 2+ and membrane voltage signals. The open probability of BK channels is regulated by the intracellular concentration of divalent cations sensed by a large structure in the BK channel called the "gating ring," which is formed by four tandems of regulator of conductance for K + (RCK1 and RCK2) domains. In contrast to Ca 2+ that binds to both RCK domains, Mg 2+ , Cd 2+ , or Ba 2+ interact preferentially with either one or the other. Interaction of cations with their binding sites causes molecular rearrangements of the gating ring, but how these motions occur remains elusive. We have assessed the separate contributions of each RCK domain to the cation-induced gating-ring structural rearrangements, using patch-clamp fluorometry. Here we show that Mg 2+ and Ba 2+ selectively induce structural movement of the RCK2 domain, whereas Cd 2+ causes motions of RCK1, in all cases substantially smaller than those elicited by Ca 2+ By combining divalent species interacting with unique sites, we demonstrate that RCK1 and RCK2 domains move independently when their specific binding sites are occupied. Moreover, binding of chemically distinct cations to both RCK domains is additive, emulating the effect of fully occupied Ca 2+ binding sites.

  20. Real-Time Observation of Order-Disorder Transformation of Organic Cations Induced Phase Transition and Anomalous Photoluminescence in Hybrid Perovskites.

    PubMed

    Yang, Bin; Ming, Wenmei; Du, Mao-Hua; Keum, Jong K; Puretzky, Alexander A; Rouleau, Christopher M; Huang, Jinsong; Geohegan, David B; Wang, Xiaoping; Xiao, Kai

    2018-05-01

    A fundamental understanding of the interplay between the microscopic structure and macroscopic optoelectronic properties of organic-inorganic hybrid perovskite materials is essential to design new materials and improve device performance. However, how exactly the organic cations affect the structural phase transition and optoelectronic properties of the materials is not well understood. Here, real-time, in situ temperature-dependent neutron/X-ray diffraction and photoluminescence (PL) measurements reveal a transformation of the organic cation CH 3 NH 3 + from order to disorder with increasing temperature in CH 3 NH 3 PbBr 3 perovskites. The molecular-level order-to-disorder transformation of CH 3 NH 3 + not only leads to an anomalous increase in PL intensity, but also results in a multidomain to single-domain structural transition. This discovery establishes the important role that organic cation ordering has in dictating structural order and anomalous optoelectronic phenomenon in hybrid perovskites. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. The formation of the dolomite-analogue norsethite: Reaction pathway and cation ordering

    NASA Astrophysics Data System (ADS)

    Pimentel, Carlos; Pina, Carlos M.

    2014-10-01

    Reaction pathways and cation ordering mechanisms involved in the formation of the mineral dolomite in nature still remain poorly understood. This is mainly due to the experimental problems posed by the synthesis of dolomite at ambient conditions, which preclude monitoring its formation in reasonable time scales. However, processes leading to the crystallization of fully-ordered dolomite-like structures can be studied by conducting experiments with mineral analogues, which are more readily precipitated. In this paper we present a study of the formation of the dolomite-analogue norsethite [BaMg(CO3)2] from a slurry which was aged at room temperature during 14 days. We found that norsethite forms by two dissolution-crystallization reactions from an initial amorphous nano-sized precipitate. The first reaction produces a mineral assemblage composed by witherite [BaCO3], northupite [Na3Mg(CO3)2Cl] and norsethite. The second dissolution-crystallization process leads to the almost complete depletion of witherite and northupite in favor of norsethite. While the composition of norsethite crystals rapidly reaches a Ba/Mg = 1 ratio, X-ray diffraction peaks indicate an increase in the crystallinity of those crystals during the first 48 h of reaction. Simultaneously, Ba-Mg cation ordering increases, as shown by the evolution of intensity ratios of certain superstructure and structure reflections. Altogether, these results demonstrate that the formation of fully-ordered norsethite occurs by a sequence of solvent-mediated processes which involve a number of precursors. Our study also suggests that similar processes might lead to the formation of dolomite in natural environments.

  2. B-Site Cation-Ordered Double-Perovskite Oxide as an Outstanding Electrode Material for Supercapacitive Energy Storage Based on the Anion Intercalation Mechanism.

    PubMed

    Xu, Zhenye; Liu, Yu; Zhou, Wei; Tade, Moses O; Shao, Zongping

    2018-03-21

    Perovskite oxides are highly promising electrodes for oxygen-ion-intercalation-type supercapacitors owing to their high oxygen vacancy concentration, oxygen diffusion rate, and tap density. Based on the anion intercalation mechanism, the capacitance is contributed by surface redox reactions and oxygen ion intercalation in the bulk materials. A high concentration of oxygen vacancies is needed because it is the main charge carrier. In this study, we propose a B-site cation-ordered Ba 2 Bi 0.1 Sc 0.2 Co 1.7 O 6-δ as an electrode material with an extremely high oxygen vacancy concentration and oxygen diffusion rate. A maximum capacitance of 1050 F g -1 was achieved, and a high capacitance of 780 F g -1 was maintained even after 3000 charge-discharge cycles at a current density of 1 A g -1 with an aqueous alkaline solution (6 M KOH) electrolyte, indicating an excellent cycling stability. In addition, the specific volumetric capacitance of Ba 2 Bi 0.1 Sc 0.2 Co 1.7 O 6-δ reaches up to 2549.4 F cm -3 based on the dense construction and high tap density (3.2 g cm -3 ). In addition, an asymmetric supercapacitor was constructed using activated carbon as a negative electrode, and it displayed the highest specific energy density of 70 Wh kg -1 at the power density of 787 W kg -1 in this study.

  3. Correlating cation ordering and voltage fade in a lithium–manganese-rich lithium-ion battery cathode oxide: a joint magnetic susceptibility and TEM study

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

    Mohanty, Debasish; Sefat, Athena S.; Li, Jianlin

    Structure–electrochemical property correlation is presented for lithium–manganese-rich layered–layered nickel manganese cobalt oxide (LMR–NMC) having composition Li1.2Co0.1Mn0.55Ni0.15O2 (TODA HE5050) in order to examine the possible reasons for voltage fade during short-to-mid-term electrochemical cycling. The Li1.2Co0.1Mn0.55Ni0.15O2 based cathodes were cycled at two different upper cutoff voltages (UCV), 4.2 V and 4.8 V, for 1, 10, and 125 cycles; voltage fade was observed after 10 and 125 cycles only when the UCV was 4.8 V. Magnetic susceptibility and selected-area electron diffraction data showed the presence of cation ordering in the pristine material, which remained after 125 cycles when the UCV was 4.2 V.more » When cycled at 4.8 V, the magnetic susceptibility results showed the suppression of cation ordering after one cycle; the cation ordering diminished upon further cycling and was not observed after 125 cycles. Selected-area electron diffraction data from oxides oriented towards the [0001] zone axis revealed a decrease in the intensity of cation-ordering reflections after one cycle and an introduction of spinel-type reflections after 10 cycles at 4.8 V; after 125 cycles, only the spinel-type reflections and the fundamental O3 layered oxide reflections were observed. A significant decrease in the effective magnetic moment of the compound after one cycle at 4.8 V indicated the presence of lithium and/or oxygen vacancies; analysis showed a reduction of Mn4+ (high spin/low spin) in the pristine oxide to Mn3+ (low spin) after one cycle. The effective magnetic moment was higher after 10 and 125 cycles at 4.8 V, suggesting the presence of Mn3+ in a high spin state, which is believed to originate from distorted spinel (Li2Mn2O4) and/or spinel (LiMn2O4) compounds. The increase in effective magnetic moments was not observed when the oxide was cycled at 4.2 V, indicating the stability of the structure under these conditions. This study shows that

  4. Aluminium substitution in iron(II-III)-layered double hydroxides: Formation and cationic order

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

    Ruby, Christian; Abdelmoula, Mustapha; Aissa, Rabha

    The formation and the modifications of the structural properties of an aluminium-substituted iron(II-III)-layered double hydroxide (LDH) of formula Fe{sub 4}{sup II}Fe{sub (2-6y)}{sup III}Al{sub 6y}{sup III} (OH){sub 12} SO{sub 4}, 8H{sub 2}O are followed by pH titration curves, Moessbauer spectroscopy and high-resolution X-ray powder diffraction using synchrotron radiation. Rietveld refinements allow to build a structural model for hydroxysulphate green rust, GR(SO{sub 4}{sup 2-}), i.e. y=0, in which a bilayer of sulphate anions points to the Fe{sup 3+} species. A cationic order is proposed to occur in both GR(SO{sub 4}{sup 2-}) and aluminium-substituted hydroxysulphate green rust when y<0.08. Variation of the cellmore » parameters and a sharp decrease in average crystal size and anisotropy are detected for an aluminium content as low as y=0.01. The formation of Al-GR(SO{sub 4}{sup 2-}) is preceded by the successive precipitation of Fe{sup III} and Al{sup III} (oxy)hydroxides. Adsorption of more soluble Al{sup III} species onto the initially formed ferric oxyhydroxide may be responsible for this slowdown of crystal growth. Therefore, the insertion of low aluminium amount (y{approx}0.01) could be an interesting way for increasing the surface reactivity of iron(II-III) LDH that maintains constant the quantity of the reactive Fe{sup II} species of the material. - Graphical abstract: (a) Crystallographical structure of sulphated green rust: SO{sub 4}{sup 2-} point to the Fe{sup 3+} cations (red) that form an ordered array with the Fe{sup 2+} cations (green). (b) Width and asymmetry of the synchrotron XRD peaks increase rapidly when some Al{sup 3+} species substitute the Fe{sup 3+} cations; z is molar ratio Al{sup 3+}/Fe{sup 3+}.« less

  5. Ordered DNA-Surfactant Hybrid Nanospheres Triggered by Magnetic Cationic Surfactants for Photon- and Magneto-Manipulated Drug Delivery and Release.

    PubMed

    Xu, Lu; Wang, Yitong; Wei, Guangcheng; Feng, Lei; Dong, Shuli; Hao, Jingcheng

    2015-12-14

    Here we construct for the first time ordered surfactant-DNA hybrid nanospheres of double-strand (ds) DNA and cationic surfactants with magnetic counterion, [FeCl3Br](-). The specificity of the magnetic cationic surfactants that can compact DNA at high concentrations makes it possible for building ordered nanospheres through aggregation, fusion, and coagulation. Cationic surfactants with conventional Br(-) cannot produce spheres under the same condition because they lose the DNA compaction ability. When a light-responsive magnetic cationic surfactant is used to produce nanospheres, a dual-controllable drug-delivery platform can be built simply by the applications of external magnetic force and alternative UV and visible light. These nanospheres obtain high drug absorption efficiency, slow release property, and good biocompatibility. There is potential for effective magnetic-field-based targeted drug delivery, followed by photocontrollable drug release. We deduce that our results might be of great interest for making new functional nucleic-acid-based nanomachines and be envisioned to find applications in nanotechnology and biochemistry.

  6. Synthesis, crystal structure and magnetic properties of a new B-site ordered double perovskite Sr{sub 2}CuIrO{sub 6}

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

    Vasala, Sami; Yamauchi, Hisao; Karppinen, Maarit, E-mail: maarit.karppinen@aalto.fi

    2014-12-15

    Here we synthesize and characterize a new double-perovskite oxide Sr{sub 2}CuIrO{sub 6}. The synthesis requires the use of high oxygen pressure to stabilize the VI oxidation state of iridium. The compound has a tetragonally-distorted crystal structure due to the Jahn–Teller active Cu{sup II} ion, and a high degree of B-site cation order. Magnetic transition is apparent at 15 K, but the zero-field-cooled and field-cooled susceptibilities diverge below this temperature. The high degree of cation order would exclude the possibility of a typical spin-glass, indicating that the divergence is probably due to a frustration of the magnetic interactions between Cu andmore » Ir, with a high frustration factor of f≈25. - Graphical abstract: A new member of the A{sub 2}B′B″O{sub 6} double-perovskite family with JT-active Cu{sup II} at the B′ site and Ir{sup VI} at the B″ site is synthesized through high pressure synthesis and characterized for the structural and magnetic properties. - Highlights: • New member of the A{sub 2}CuB″O{sub 6} double-perovskite family is synthesized with B″=Ir. • Stabilization of Ir{sup VI} requires the use of high oxygen pressure synthesis. • Crystal structure is tetragonally distorted due to JT-active Cu{sup II}. • Divergence of ZFC and FC curves is seen below the T{sub N} of 15 K. • This is presumably due to a frustration effect.« less

  7. The role of the peripheral anionic site and cation-pi interactions in the ligand penetration of the human AChE gorge.

    PubMed

    Branduardi, Davide; Gervasio, Francesco Luigi; Cavalli, Andrea; Recanatini, Maurizio; Parrinello, Michele

    2005-06-29

    We study the ligand (tetramethylammonium) recognition by the peripheral anionic site and its penetration of the human AChE gorge by using atomistic molecular dynamics simulations and our recently developed metadynamics method. The role of both the peripheral anionic site and the formation of cation-pi interactions in the ligand entrance are clearly shown. In particular, a simulation with the W286A mutant shows the fundamental role of this residue in anchoring the ligand at the peripheral anionic site of the enzyme and in positioning it prior to the gorge entrance. Once the ligand is properly oriented, the formation of specific and synchronized cation-pi interactions with W86, F295, and Y341 enables the gorge penetration. Eventually, the ligand is stabilized in a free energy basin by means of cation-pi interactions with W86.

  8. Membrane Order Is a Key Regulator of Divalent Cation-Induced Clustering of PI(3,5)P2 and PI(4,5)P2.

    PubMed

    Sarmento, Maria J; Coutinho, Ana; Fedorov, Aleksander; Prieto, Manuel; Fernandes, Fábio

    2017-10-31

    Although the evidence for the presence of functionally important nanosized phosphorylated phosphoinositide (PIP)-rich domains within cellular membranes has accumulated, very limited information is available regarding the structural determinants for compartmentalization of these phospholipids. Here, we used a combination of fluorescence spectroscopy and microscopy techniques to characterize differences in divalent cation-induced clustering of PI(4,5)P 2 and PI(3,5)P 2 . Through these methodologies we were able to detect differences in divalent cation-induced clustering efficiency and cluster size. Ca 2+ -induced PI(4,5)P 2 clusters are shown to be significantly larger than the ones observed for PI(3,5)P 2 . Clustering of PI(4,5)P 2 is also detected at physiological concentrations of Mg 2+ , suggesting that in cellular membranes, these molecules are constitutively driven to clustering by the high intracellular concentration of divalent cations. Importantly, it is shown that lipid membrane order is a key factor in the regulation of clustering for both PIP isoforms, with a major impact on cluster sizes. Clustered PI(4,5)P 2 and PI(3,5)P 2 are observed to present considerably higher affinity for more ordered lipid phases than the monomeric species or than PI(4)P, possibly reflecting a more general tendency of clustered lipids for insertion into ordered domains. These results support a model for the description of the lateral organization of PIPs in cellular membranes, where both divalent cation interaction and membrane order are key modulators defining the lateral organization of these lipids.

  9. A -cation control of magnetoelectric quadrupole order in A (TiO)Cu 4(PO4)4(A =Ba ,Sr, and Pb)

    NASA Astrophysics Data System (ADS)

    Kimura, K.; Toyoda, M.; Babkevich, P.; Yamauchi, K.; Sera, M.; Nassif, V.; Rønnow, H. M.; Kimura, T.

    2018-04-01

    Ferroic magnetic quadrupole order exhibiting macroscopic magnetoelectric activity is discovered in the novel compound A (TiO ) Cu4(PO4)4 with A = Pb, which is in contrast with antiferroic quadrupole order observed in the isostructural compounds with A = Ba and Sr. Unlike the famous lone-pair stereochemical activity which often triggers ferroelectricity as in PbTiO3, the Pb2 + cation in Pb (TiO ) Cu4(PO4)4 is stereochemically inactive but dramatically alters specific magnetic interactions and consequently switches the quadrupole order from antiferroic to ferroic. Our first-principles calculations uncover a positive correlation between the degree of A -O bond covalency and a stability of the ferroic quadrupole order.

  10. Characterization of ordering in A-site deficient perovskite Ca 1–xLa 2x/3TiO 3 using STEM/EELS

    DOE PAGES

    Danaie, Mohsen; Kepaptsoglou, Demie; Ramasse, Quentin M.; ...

    2016-09-15

    The vacancy ordering behavior of an A-site deficient perovskite system, Ca 1–xLa 2x/3TiO 3, was studied using atomic resolution scanning transmission electron microscopy (STEM) in conjunction with electron energy-loss spectroscopy (EELS), with the aim of determining the role of A-site composition changes. At low La content (x = 0.2), adopting Pbnm symmetry, there was no indication of long-range ordering. Domains, with clear boundaries, were observed in bright-field (BF) imaging, but were not immediately visible in the corresponding high-angle annular dark-field (HAADF) image. These boundaries, with the aid of displacement maps from A-site cations in the HAADF signal, are shown tomore » be tilt boundaries. At the La-rich end of the composition (x = 0.9), adopting Cmmm symmetry, long-range ordering of vacancies and La 3+ ions was observed, with alternating La-rich and La-poor layers on (001)p planes, creating a double perovskite lattice along the c axis. These highly ordered domains can be found isolated within a random distribution of vacancies/La 3+, or within a large population, encompassing a large volume. In regions with a high number density of double perovskite domains, these highly ordered domains were separated by twin boundaries, with 90° or 180° lattice rotations across boundaries. In conclusion, the occurrence and characteristics of these ordered structures are discussed and compared with similar perovskite systems.« less

  11. In Situ Probing and Synthetic Control of Cationic Ordering in Ni-Rich Layered Oxide Cathodes

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

    Zhao, Jianqing; Zhang, Wei; Huq, Ashfia

    Ni-rich layered oxides (LiNi1-xMxO2; M = Co, Mn, ...) are appealing alternatives to conventional LiCoO2 as cathodes in Li-ion batteries for automobile and other large-scale applications due to their high theoretical capacity and low cost. However, preparing stoichiometric LiNi1-xMxO2 with ordered layer structure and high reversible capacity, has proven difficult due to cation mixing in octahedral sites. Herein, in situ studies of synthesis reactions and the associated structural ordering in preparing LiNiO2 and the Co-substituted variant, LiNi0.8Co0.2O2, are made, to gain insights into synthetic control of the structure and electrochemical properties of Ni-rich layered oxides. Results from this study indicatemore » a direct transformation of the intermediate from the rock salt structure into hexagonal phase, and during the process, Co substitution facilities the nucleation of a Co-rich layered phase at low temperatures and subsequent growth and stabilization of solid solution Li(Ni, Co)O-2 upon further heat treatment. Optimal conditions are identified from the in situ studies and utilized to obtain stoichiometric LiNi0.8Co0.2O2 that exhibits high capacity (up to 200 mA h g(-1) ) with excellent retention. The findings shed light on designing high performance Ni-rich layered oxide cathodes through synthetic control of the structural ordering in the materials.« less

  12. Liquid-like cationic sub-lattice in copper selenide clusters

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

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

  13. Cation ordering/disordering kinetics in Ba3CoNb2O9: An in situ study using synchrotron x-ray powder diffraction

    NASA Astrophysics Data System (ADS)

    Mallinson, P. M.; Claridge, J. B.; Rosseinsky, M. J.; Ibberson, R. M.; Wright, J. P.; Fitch, A. N.; Price, T.; Iddles, D. M.

    2007-11-01

    In situ synchrotron x-ray powder diffraction has been used to study the kinetics of cation ordering and disordering in the microwave dielectric electroceramic Ba3CoNb2O9 with a time resolution of 15s. The method enables the order/disorder temperature (To /d) in this material of 1430°C to be directly observed. The changes in the rate and degree of cation ordering and in the growth of ordered domains between samples ordered from standard precursor material and then subsequently reordered following an annealing period above To /d show that small changes in precursor order state and phase assemblage strongly influence the final domain size.

  14. Distinct roles of beta1 metal ion-dependent adhesion site (MIDAS), adjacent to MIDAS (ADMIDAS), and ligand-associated metal-binding site (LIMBS) cation-binding sites in ligand recognition by integrin alpha2beta1.

    PubMed

    Valdramidou, Dimitra; Humphries, Martin J; Mould, A Paul

    2008-11-21

    Integrin-ligand interactions are regulated in a complex manner by divalent cations, and previous studies have identified ligand-competent, stimulatory, and inhibitory cation-binding sites. In collagen-binding integrins, such as alpha2beta1, ligand recognition takes place exclusively at the alpha subunit I domain. However, activation of the alphaI domain depends on its interaction with a structurally similar domain in the beta subunit known as the I-like or betaI domain. The top face of the betaI domain contains three cation-binding sites: the metal-ion dependent adhesion site (MIDAS), the ADMIDAS (adjacent to MIDAS), and LIMBS (ligand-associated metal-binding site). The role of these sites in controlling ligand binding to the alphaI domain has yet to be elucidated. Mutation of the MIDAS or LIMBS completely blocked collagen binding to alpha2beta1; in contrast mutation of the ADMIDAS reduced ligand recognition but this effect could be overcome by the activating monoclonal antibody TS2/16. Hence, the MIDAS and LIMBS appear to be essential for the interaction between alphaI and betaI, whereas occupancy of the ADMIDAS has an allosteric effect on the conformation of betaI. An activating mutation in the alpha2 I domain partially restored ligand binding to the MIDAS and LIMBS mutants. Analysis of the effects of Ca(2+), Mg(2+), and Mn(2+) on ligand binding to these mutants showed that the MIDAS is a ligand-competent site through which Mn(2+) stimulates ligand binding, whereas the LIMBS is a stimulatory Ca(2+)-binding site, occupancy of which increases the affinity of Mg(2+) for the MIDAS.

  15. Cation disorder in shocked orthopyroxene.

    NASA Technical Reports Server (NTRS)

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

    1971-01-01

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

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

    PubMed

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

    2017-06-06

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

  17. In Situ Probing and Synthetic Control of Cationic Ordering in Ni-Rich Layered Oxide Cathodes

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

    Zhao, Jianqing; Zhang, Wei; Huq, Ashfia

    Ni-rich layered oxides (LiNi 1-xM xO 2; M=Co, Mn, …) are appealing alternatives to conventional LiCoO 2 as cathodes in Li-ion batteries for automobile and other large-scale applications due to their high theoretical capacity and low cost. However, preparing stoichiometric LiNi 1-xM xO 2 with ordered layer structure and high reversible capacity, has proven difficult due to Ni 2+/Li + cation mixing in octahedral sites. Herein, we report on in-situ studies of synthesis reactions and the associated structural ordering in preparing LiNiO 2 and the Co-substituted variant, LiNi 0.8Co 0.2O 2, thereby gaining insights into synthetic control of the structuremore » and electrochemical properties of Ni-rich layered oxides. Results from this study indicate a direct transformation of the intermediate from the rock salt structure into hexagonal phase, and during the process, Co substitution facilities the nucleation of a Co-rich layered phase at low temperatures and subsequent growth and stabilization of solid solution Li(Ni, Co)O 2 upon heat treatment in a highly oxidation environment. Optimal conditions were identified from the in-situ studies and utilized in obtaining stoichiometric LiNi 0.8Co 0.2O 2 that exhibits high capacity of about 200 mAh/g with excellent retention. The findings shed light on designing Ni-rich layered oxide cathodes with enhanced electrochemical properties through synthetic control of the structural ordering in the materials.« less

  18. In Situ Probing and Synthetic Control of Cationic Ordering in Ni-Rich Layered Oxide Cathodes

    DOE PAGES

    Zhao, Jianqing; Zhang, Wei; Huq, Ashfia; ...

    2016-10-17

    Ni-rich layered oxides (LiNi 1-xM xO 2; M=Co, Mn, …) are appealing alternatives to conventional LiCoO 2 as cathodes in Li-ion batteries for automobile and other large-scale applications due to their high theoretical capacity and low cost. However, preparing stoichiometric LiNi 1-xM xO 2 with ordered layer structure and high reversible capacity, has proven difficult due to Ni 2+/Li + cation mixing in octahedral sites. Herein, we report on in-situ studies of synthesis reactions and the associated structural ordering in preparing LiNiO 2 and the Co-substituted variant, LiNi 0.8Co 0.2O 2, thereby gaining insights into synthetic control of the structuremore » and electrochemical properties of Ni-rich layered oxides. Results from this study indicate a direct transformation of the intermediate from the rock salt structure into hexagonal phase, and during the process, Co substitution facilities the nucleation of a Co-rich layered phase at low temperatures and subsequent growth and stabilization of solid solution Li(Ni, Co)O 2 upon heat treatment in a highly oxidation environment. Optimal conditions were identified from the in-situ studies and utilized in obtaining stoichiometric LiNi 0.8Co 0.2O 2 that exhibits high capacity of about 200 mAh/g with excellent retention. The findings shed light on designing Ni-rich layered oxide cathodes with enhanced electrochemical properties through synthetic control of the structural ordering in the materials.« less

  19. B-site cation order/disorder and their valence states in Ba3MnNb2O9 perovskite oxide

    NASA Astrophysics Data System (ADS)

    Xin, Yan; Huang, Qing; Shafieizadeh, Zahra; Zhou, Haidong

    2018-06-01

    Polycrystalline samples Ba3MnNb2O9 synthesized by solid state reaction and single crystal samples grown by optical floating zone have been characterized using scanning transmission electron microscopy and electron energy loss spectroscopy. Three types of B-site Mn and Nb ordering phase are observed: fully ordered 1Mn:2Nb; fully disordered; nano-sized 1Mn:1Nb ordered. No electronic structure change for crystals with different ordering/disordering. The Mn valence is determined to be 2+, and Nb valence is 5+. Oxygen 2p orbitals hybridize with Mn 3d and Nb 4d orbitals. Factors that affect the electron energy loss near edge structures of transition metal white-lines in electron energy loss spectroscopy are explicitly illustrated and discussed.

  20. Interplay of Cation Ordering and Ferroelectricity in Perovskite Tin Iodides: Designing a Polar Halide Perovskite for Photovoltaic Applications

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

    Gou, Gaoyang; Young, Joshua; Liu, Xian

    2016-09-28

    Owing to its ideal semiconducting band gap and good carrier transport properties, the fully inorganic perovskite CsSnI 3 has been proposed as a visible-light absorber for photovoltaic (PV) applications. However, compared to the organic inorganic lead halide perovskite CH 3NH 3PbI 3, CsSnI 3 solar cells display very low energy conversion efficiency. In this work, we propose a potential route to improve the PV properties of CsSnI 3. Using first-principles calculations, we examine the crystal structures and electronic properties of CsSnI 3, including its structural polymorphs. Next, we purposefully order Cs and Rb cations on the A site to createmore » the double perovskite (CsRb)Sn 2I 6. We find that a stable ferroelectric polarization arises from the nontrivial coupling between polar displacements and octahedral rotations of the SnI 6 network. These ferroelectric double perovskites are predicted to have energy band gaps and carrier effective masses similar to those of CsSnI 3. More importantly, unlike nonpolar CsSnI 3, the electric polarization present in ferroelectric (CsRb)Sn 2I 6 can effectively separate the photoexcited carriers, leading to novel ferroelectric PV materials with,potentially enhanced energy conversion efficiency.« less

  1. Increasing Base Cations in Streams: Another Legacy of Deicing Salts?

    NASA Astrophysics Data System (ADS)

    Helton, A. M.; Barclay, J. R.; Bellucci, C.; Rittenhouse, C.

    2017-12-01

    Elevated use of deicing salts directly increases sodium chloride inputs to watersheds. Sodium can accumulate in soils over time and has the potential to leach other cations (e.g., calcium, magnesium, and potassium) from the soil through cation exchange. We hypothesize that increased use of deicing salts results in a legacy of soils depleted in non-sodium base cations with loss of cations to receiving waters. The goal of this project is to quantify temporal trends in base cations and chloride in streams and rivers across the United States. We used Weighted Regressions on Time, Discharge, and Season (WRTDS) to analyze trends in base cations. Our preliminary analysis of 10 rivers in Connecticut with chemical periods of record ranging from 24 - 64 years (median = 55 years), shows that the flux of base cations is increasing in all sites (25 - 366 103 meq ha-1 yr-1 yr-1), driven largely by increases in sodium (23 - 222 103 meq ha-1 yr-1 yr-1), the dominant cation in 7 of the sites. Chloride is also increasing at all sites (26 - 261 103 meq ha-1 yr-1 yr-1), which, in combination with salt use trends, suggests a road salt source for the increased sodium. Non-sodium cations are also increasing in 9 of the sites (8 - 54 103 meq ha-1 yr-1 yr-1), though they are not directly added with most deicing salts. We will compare these trends to other long-term sites across the United States, and quantify relationships between cation trends and land cover, road density, and snowfall.

  2. Partitioning of dopant cations between β-tricalcium phosphate and fluorapatite

    NASA Astrophysics Data System (ADS)

    Jay, E. E.; Mallinson, P. M.; Fong, S. K.; Metcalfe, B. L.; Grimes, R. W.

    2011-07-01

    Mixed crystalline phase composite ceramics offer the possibility of partitioning defect species between the phases as well as occupancy of specific sites within a given phase. Here we use atomic scale simulations to study the site preference of an extensive range of divalent and trivalent substitutional ions across the five cation sites in β-tricalcium phosphate ( β-TCP) and the two cations sites in fluorapatite (FAp). This study indicates that in β-TCP small dopant species occupy the smaller of the five cation sites and vice versa. Conversely, in FAp, small divalent species occupy the nominally larger Ca(1) site while larger cations occupy the Ca(2) site. Partition energies between the two phases indicate that divalent species strongly segregate to β-TCP as do Al 3+ and Ga 3+, whereas all other (larger) trivalent ions exhibit little preference.

  3. Neutral glycoconjugated amide-based calix[4]arenes: complexation of alkali metal cations in water.

    PubMed

    Cindro, Nikola; Požar, Josip; Barišić, Dajana; Bregović, Nikola; Pičuljan, Katarina; Tomaš, Renato; Frkanec, Leo; Tomišić, Vladislav

    2018-02-07

    Cation complexation in water presents a unique challenge in calixarene chemistry, mostly due to the fact that a vast majority of calixarene-based cation receptors is not soluble in water or their solubility has been achieved by introducing functionalities capable of (de)protonation. Such an approach inevitably involves the presence of counterions which compete with target cations for the calixarene binding site, and also rather often requires the use of ion-containing buffer solutions in order to control the pH. Herein we devised a new strategy towards the solution of this problem, based on introducing carbohydrate units at the lower or upper rim of calix[4]arenes which comprise efficient cation binding sites. In this context, we prepared neutral, water-soluble receptors with secondary or tertiary amide coordinating groups, and studied their complexation with alkali metal cations in aqueous and methanol (for the comparison purpose) solutions. Complexation thermodynamics was quantitatively characterized by UV spectrometry and isothermal titration calorimetry, revealing that one of the prepared tertiary amide derivatives is capable of remarkably efficient (log K ≈ 5) and selective binding of sodium cations among alkali metal cations in water. Given the ease of the synthetic procedure used, and thus the variety of accessible analogues, this study can serve as a platform for the development of reagents for diverse purposes in aqueous media.

  4. U(VI) uranyl cation-cation interactions in framework germanates.

    PubMed

    Morrison, Jessica M; Moore-Shay, Laura J; Burns, Peter C

    2011-03-21

    The isomorphous compounds NH(4)[(UO(6))(2)(UO(2))(9)(GeO(4))(GeO(3)(OH))] (1), K[(UO(6))(2)(UO(2))(9)(GeO(4))(GeO(3)(OH))] (2), Li(3)O[(UO(6))(2)(UO(2))(9)(GeO(4))(GeO(3)(OH))] (3), and Ba[(UO(6))(2)(UO(2))(9)(GeO(4))(2)] (4) were synthesized by hydrothermal reaction at 220 °C. The structures were determined using single crystal X-ray diffraction and refined to R(1) = 0.0349 (1), 0.0232 (2), 0.0236 (3), 0.0267 (4). Each are trigonal, P(3)1c. 1: a = 10.2525(5), c = 17.3972(13), V = 1583.69(16) Å(3), Z = 2; 2: a = 10.226(4), c = 17.150(9), V = 1553.1(12) Å(3), Z = 2; 3: a = 10.2668(5), c = 17.0558(11), V = 1556.94(15) Å(3), Z = 2; 4: a = 10.2012(5), c = 17.1570(12), V = 1546.23(15) Å(3), Z = 2. There are three symmetrically independent U sites in each structure, two of which correspond to typical (UO(2))(2+) uranyl ions and the other of which is octahedrally coordinated by six O atoms. One of the uranyl ions donates a cation-cation interaction, and accepts a different cation-cation interaction. The linkages between the U-centered polyhedra result in a relatively dense three-dimensional framework. Ge and low-valence sites are located within cavities in the framework of U-polyhedra. Chemical, thermal, and spectroscopic characterizations are provided.

  5. DISTINCT ROLES OF β1 MIDAS, ADMIDAS AND LIMBS CATION-BINDING SITES IN LIGAND RECOGNITION BY INTEGRIN α2β1*

    PubMed Central

    Valdramidou, Dimitra; Humphries, Martin J.; Mould, A. Paul

    2012-01-01

    Integrin-ligand interactions are regulated in a complex manner by divalent cations, and previous studies have identified ligand-competent, stimulatory, and inhibitory cation-binding sites. In collagen-binding integrins, such as α2β1, ligand recognition takes place exclusively at the α subunit I domain. However, activation of the αI domain depends on its interaction with a structurally similar domain in the β subunit known as the I-like or βI domain. The top face of the βI domain contains three cation-binding sites: the metal-ion dependent adhesion site (MIDAS), the ADMIDAS (adjacent to MIDAS) and LIMBS (ligand-associated metal binding site). The role of these sites in controlling ligand binding to the αI domain has yet to be elucidated. Mutation of the MIDAS or LIMBS completely blocked collagen binding to α2β1; in contrast mutation of the ADMIDAS reduced ligand recognition but this effect could be overcome by the activating mAb TS2/16. Hence, the MIDAS and LIMBS appear to be essential for the interaction between αI and βI whereas occupancy of the ADMIDAS has an allosteric effect on the conformation of βI. An activating mutation in the α2 I domain partially restored ligand binding to the MIDAS and LIMBS mutants. Analysis of the effects of Ca2+, Mg2+ and Mn2+ on ligand binding to these mutants showed that the MIDAS is a ligand-competent site through which Mn2+ stimulates ligand binding, whereas the LIMBS is a stimulatory Ca2+-binding site, occupancy of which increases the affinity of Mg2+ for the MIDAS. PMID:18820259

  6. Cation mobility and the sorption of chloroform in zeolite NaY: molecular dynamics study.

    PubMed

    Ramsahye, Naseem A; Bell, Robert G

    2005-03-17

    Molecular dynamics simulations at temperatures of 270, 330, and 390 K have been carried out to address the question of cation migration upon chloroform sorption in sodium zeolite Y. The results show that sodium cations located in different sites exhibit different types of mobility. These may be summarized as follows: (1) SII cations migrate toward the center of the supercage upon sorption, due to interactions with the polar sorbate molecules. (2) SI' cations hop from the sodalite cage into the supercage to fill vacant SII sites. (3) SI' cations migrate to other SI' sites within the same sodalite cage. (4) SI cations hop out of the double six-rings into SI' sites. In some instances, concerted motion of cations is observed. Furthermore, former SI' and SI cations, having crossed to SII sites, may then further migrate within the supercage, as in (1). The cation motion is dependent on the level of sorbate loading, with 10 molecules per unit cell not being enough to induce significant cation displacements, whereas the sorption of 40 molecules per unit cell results in a number of cations being displaced from their original positions. Further rearrangement of the cation positions is observed upon evacuation of the simulation cell, with some cations reverting back to sites normally occupied in bare NaY.

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

    NASA Astrophysics Data System (ADS)

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

    2018-01-01

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

  8. Understanding the Effect of Cation Disorder on the Voltage Profile of Lithium Transition-Metal Oxides

    DOE PAGES

    Abdellahi, Aziz; Urban, Alexander; Dacek, Stephen; ...

    2016-07-13

    Cation disorder is a phenomenon that is becoming increasingly important for the design of high-energy lithium transition metal oxide cathodes (LiMO 2) for Li-ion batteries. Disordered Li-excess rocksalts have recently been shown to achieve high reversible capacity, while in operando cation disorder has been observed in a large class of ordered compounds. The voltage slope (dV/dx u )is a critical quantity for the design of cation-disordered rocksalts, as it controls the Li capacity accessible at voltages below the stability limit of the electrolyte (~4.5-4.7 V). In this study, we develop a lattice model based on first principles to understand andmore » quantify the voltage slope of cation-disordered LiMO 2. We show that cation disorder increases the voltage slope of Li transition metal oxides by creating a statistical distribution of transition metal environments around Li sites, as well as by allowing Li occupation of highvoltage tetrahedral sites. We further demonstrate that the voltage slope increase upon disorder is generally smaller for highvoltage transition metals than for low-voltage transition metals due to a more effective screening of Li-M interactions by oxygen electrons. Short-range order in practical disordered compounds is found to further mitigate the voltage slope increase upon disorder. In conclusion, our analysis shows that the additional high-voltage tetrahedral capacity induced by disorder is smaller in Liexcess compounds than in stoichiometric LiMO 2 compounds.« less

  9. Kinetics of Cation and Oxyanion Adsorption and Desorption on Ferrihydrite: Roles of Ferrihydrite Binding Sites and a Unified Model

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

    Tian, Lei; Shi, Zhenqing; Lu, Yang

    Understanding the kinetics of toxic ion reactions with ferrihydrite is crucial for predicting the dynamic behavior of contaminants in soil environments. In this study, the kinetics of As(V), Cr(VI), Cu, and Pb adsorption and desorption on ferrihydrite were investigated with a combination of laboratory macroscopic experiments, microscopic investigation and mechanistic modeling. The rates of As(V), Cr(VI), Cu, and Pb adsorption and desorption on ferrihydrite, as systematically studied using a stirred-flow method, was highly dependent on the reaction pH and metal concentrations and varied significantly among four metals. Spherical aberration-corrected scanning transmission electron microscopy (Cs-STEM) showed, at sub-nano scales, all fourmore » metals were distributed within the ferrihydrite particle aggregates homogeneously after adsorption reactions, with no evidence of surface diffusion-controlled processes. Based on experimental results, we developed a unifying kinetics model for both cation and oxyanion adsorption/desorption on ferrihydrite based on the mechanistic-based equilibrium model CD-MUSIC. Overall, the model described the kinetic results well, and we quantitatively demonstrated how the equilibrium properties of the cation and oxyanion binding to various ferrihydrite sites affected the adsorption and desorption rates. Our results provided a unifying quantitative modeling method for the kinetics of both cation and oxyanion adsorption/desorption on iron minerals.« less

  10. Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes.

    PubMed

    Wang, Dawei; Kou, Ronghui; Ren, Yang; Sun, Cheng-Jun; Zhao, Hu; Zhang, Ming-Jian; Li, Yan; Huq, Ashifia; Ko, J Y Peter; Pan, Feng; Sun, Yang-Kook; Yang, Yong; Amine, Khalil; Bai, Jianming; Chen, Zonghai; Wang, Feng

    2017-10-01

    Nickel-rich layered transition metal oxides, LiNi 1- x (MnCo) x O 2 (1-x ≥ 0.5), are appealing candidates for cathodes in next-generation lithium-ion batteries (LIBs) for electric vehicles and other large-scale applications, due to their high capacity and low cost. However, synthetic control of the structural ordering in such a complex quaternary system has been a great challenge, especially in the presence of high Ni content. Herein, synthesis reactions for preparing layered LiNi 0.7 Mn 0.15 Co 0.15 O 2 (NMC71515) by solid-state methods are investigated through a combination of time-resolved in situ high-energy X-ray diffraction and absorption spectroscopy measurements. The real-time observation reveals a strong temperature dependence of the kinetics of cationic ordering in NMC71515 as a result of thermal-driven oxidation of transition metals and lithium/oxygen loss that concomitantly occur during heat treatment. Through synthetic control of the kinetic reaction pathway, a layered NMC71515 with low cationic disordering and a high reversible capacity is prepared in air. The findings may help to pave the way for designing high-Ni layered oxide cathodes for LIBs. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes

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

    Wang, Dawei; Kou, Ronghui; Ren, Yang

    Nickel-rich layered transition metal oxides, LiNi 1-x(MnCo) xO 2 (1-x ≥ 0.5), are appealing candidates for cathodes in next-generation lithium-ion batteries (LIBs) for electric vehicles and other large-scale applications, due to their high capacity and low cost. However, synthetic control of the structural ordering in such a complex quaternary system has been a great challenge, especially in the presence of high Ni content. Herein, synthesis reactions for preparing layered LiNi 0.7Mn 0.15Co 0.15O 2 (NMC71515) by solid-state methods are investigated through a combination of time-resolved in situ high-energy X-ray diffraction and absorption spectroscopy measurements. The real-time observation reveals a strongmore » temperature dependence of the kinetics of cationic ordering in NMC71515 as a result of thermal-driven oxidation of transition metals and lithium/oxygen loss that concomitantly occur during heat treatment. Through synthetic control of the kinetic reaction pathway, a layered NMC71515 with low cationic disordering and a high reversible capacity is prepared in air. The findings may help to pave the way for designing high-Ni layered oxide cathodes for LIBs« less

  12. Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes

    DOE PAGES

    Wang, Dawei; Kou, Ronghui; Ren, Yang; ...

    2017-08-25

    Nickel-rich layered transition metal oxides, LiNi 1-x(MnCo) xO 2 (1-x ≥ 0.5), are appealing candidates for cathodes in next-generation lithium-ion batteries (LIBs) for electric vehicles and other large-scale applications, due to their high capacity and low cost. However, synthetic control of the structural ordering in such a complex quaternary system has been a great challenge, especially in the presence of high Ni content. Herein, synthesis reactions for preparing layered LiNi 0.7Mn 0.15Co 0.15O 2 (NMC71515) by solid-state methods are investigated through a combination of time-resolved in situ high-energy X-ray diffraction and absorption spectroscopy measurements. The real-time observation reveals a strongmore » temperature dependence of the kinetics of cationic ordering in NMC71515 as a result of thermal-driven oxidation of transition metals and lithium/oxygen loss that concomitantly occur during heat treatment. Through synthetic control of the kinetic reaction pathway, a layered NMC71515 with low cationic disordering and a high reversible capacity is prepared in air. The findings may help to pave the way for designing high-Ni layered oxide cathodes for LIBs« less

  13. Cation exchange in a glacial till drumlin at a road salt storage facility

    NASA Astrophysics Data System (ADS)

    Ostendorf, David W.; Xing, Baoshan; Kallergis, Niki

    2009-05-01

    We use laboratory and field data to calibrate existing geochemical and transport models of cation exchange induced by contamination of an unconfined aquifer at a road salt storage facility built upon a glacial till drumlin in eastern Massachusetts. A Gaines and Thomas selectivity coefficient K models the equilibrium sodium and divalent cation distribution in the groundwater and solid matrix, while an existing method of characteristics model describes the advective transport of total dissolved cations and sorbed sodium. Laboratory isotherms of split spoon soil samples from the drumlin calibrate K with an average value of 0.0048 (L/g) 1/2 for a measured cation exchange capacity of 0.057 meq/g dry soil. Ten years of monitoring well data document groundwater flow and the advection of conservative chloride due to outdoor storage and handling of road salt at the site. The monitoring well cation data and retarded transport model offer an independent K calibration of 0.0040 to 0.0047 (L/g) 1/2: the consistency of the field and laboratory selectivity coefficient calibrations endorse this application of the Gaines and Thomas and method of characteristics models. The advancing deicing agent plume releases divalent cations from the till into the groundwater, so that monitoring well samples do not reflect the chemical composition of the road salt. In this regard, dissolved divalent cation milliequivalent concentrations are as high as 80% of the total dissolved cationic concentrations in the salt contaminated monitoring well samples, far greater than their 2.5% level in the road salt stored at the site. Cation exchange can thus obscure attempts to hindcast stored road salt sodium water table concentration from monitoring well sample stoichiometry, or to predict sodium impacts on groundwater or receiving stream quality downgradient of the well.

  14. Cation exchange in a glacial till drumlin at a road salt storage facility.

    PubMed

    Ostendorf, David W; Xing, Baoshan; Kallergis, Niki

    2009-05-12

    We use laboratory and field data to calibrate existing geochemical and transport models of cation exchange induced by contamination of an unconfined aquifer at a road salt storage facility built upon a glacial till drumlin in eastern Massachusetts. A Gaines and Thomas selectivity coefficient K models the equilibrium sodium and divalent cation distribution in the groundwater and solid matrix, while an existing method of characteristics model describes the advective transport of total dissolved cations and sorbed sodium. Laboratory isotherms of split spoon soil samples from the drumlin calibrate K with an average value of 0.0048 (L/g)(1/2) for a measured cation exchange capacity of 0.057 meq/g dry soil. Ten years of monitoring well data document groundwater flow and the advection of conservative chloride due to outdoor storage and handling of road salt at the site. The monitoring well cation data and retarded transport model offer an independent K calibration of 0.0040 to 0.0047 (L/g)(1/2): the consistency of the field and laboratory selectivity coefficient calibrations endorse this application of the Gaines and Thomas and method of characteristics models. The advancing deicing agent plume releases divalent cations from the till into the groundwater, so that monitoring well samples do not reflect the chemical composition of the road salt. In this regard, dissolved divalent cation milliequivalent concentrations are as high as 80% of the total dissolved cationic concentrations in the salt contaminated monitoring well samples, far greater than their 2.5% level in the road salt stored at the site. Cation exchange can thus obscure attempts to hindcast stored road salt sodium water table concentration from monitoring well sample stoichiometry, or to predict sodium impacts on groundwater or receiving stream quality downgradient of the well.

  15. Enhanced oxygen storage capacity of cation-ordered cerium-zirconium oxide induced by titanium substitution.

    PubMed

    Goto, Yoshihiro; Morikawa, Akira; Iwasaki, Masaoki; Miura, Masahide; Tanabe, Toshitaka

    2018-04-03

    Herein, we report on the synthesis of Ce0.5Zr0.5-xTixO2 oxygen storage materials prepared via a solution combustion method. Ce0.5Zr0.4Ti0.1O2 showed an outstanding oxygen storage capacity (1310 μmol-O per g) at 200 °C compared to conventional κ-Ce2Zr2O8 (650 μmol-O per g) due to its cation ordering and the formation of weakly bound oxygen atoms induced by Ti substitution.

  16. Cations Stiffen Actin Filaments by Adhering a Key Structural Element to Adjacent Subunits

    PubMed Central

    2016-01-01

    Ions regulate the assembly and mechanical properties of actin filaments. Recent work using structural bioinformatics and site-specific mutagenesis favors the existence of two discrete and specific divalent cation binding sites on actin filaments, positioned in the long axis between actin subunits. Cation binding at one site drives polymerization, while the other modulates filament stiffness and plays a role in filament severing by the regulatory protein, cofilin. Existing structural methods have not been able to resolve filament-associated cations, and so in this work we turn to molecular dynamics simulations to suggest a candidate binding pocket geometry for each site and to elucidate the mechanism by which occupancy of the “stiffness site” affects filament mechanical properties. Incorporating a magnesium ion in the “polymerization site” does not seem to require any large-scale change to an actin subunit’s conformation. Binding of a magnesium ion in the “stiffness site” adheres the actin DNase-binding loop (D-loop) to its long-axis neighbor, which increases the filament torsional stiffness and bending persistence length. Our analysis shows that bound D-loops occupy a smaller region of accessible conformational space. Cation occupancy buries key conserved residues of the D-loop, restricting accessibility to regulatory proteins and enzymes that target these amino acids. PMID:27146246

  17. Epitaxially stabilized iridium spinel oxide without cations in the tetrahedral site

    NASA Astrophysics Data System (ADS)

    Kuriyama, Hiromichi; Matsuno, Jobu; Niitaka, Seiji; Uchida, Masaya; Hashizume, Daisuke; Nakao, Aiko; Sugimoto, Kunihisa; Ohsumi, Hiroyuki; Takata, Masaki; Takagi, Hidenori

    2010-05-01

    Single-crystalline thin film of an iridium dioxide polymorph Ir2O4 has been fabricated by the pulsed laser deposition of LixIr2O4 precursor and the subsequent Li-deintercalation using soft chemistry. Ir2O4 crystallizes in a spinel (AB2O4) without A cations in the tetrahedral site, which is isostructural to λ-MnO2. Ir ions form a pyrochlore sublattice, which is known to give rise to a strong geometrical frustration. This Ir spinel was found to be a narrow gap insulator, in remarkable contrast to the metallic ground state of rutile-type IrO2. We argue that an interplay of a strong spin-orbit coupling and a Coulomb repulsion gives rise to an insulating ground state as in a layered perovskite Sr2IrO4.

  18. Identification of a divalent metal cation binding site in herpes simplex virus 1 (HSV-1) ICP8 required for HSV replication.

    PubMed

    Bryant, Kevin F; Yan, Zhipeng; Dreyfus, David H; Knipe, David M

    2012-06-01

    Herpes simplex virus 1 (HSV-1) ICP8 is a single-stranded DNA-binding protein that is necessary for viral DNA replication and exhibits recombinase activity in vitro. Alignment of the HSV-1 ICP8 amino acid sequence with ICP8 homologs from other herpesviruses revealed conserved aspartic acid (D) and glutamic acid (E) residues. Amino acid residue D1087 was conserved in every ICP8 homolog analyzed, indicating that it is likely critical for ICP8 function. We took a genetic approach to investigate the functions of the conserved ICP8 D and E residues in HSV-1 replication. The E1086A D1087A mutant form of ICP8 failed to support the replication of an ICP8 mutant virus in a complementation assay. E1086A D1087A mutant ICP8 bound DNA, albeit with reduced affinity, demonstrating that the protein is not globally misfolded. This mutant form of ICP8 was also recognized by a conformation-specific antibody, further indicating that its overall structure was intact. A recombinant virus expressing E1086A D1087A mutant ICP8 was defective in viral replication, viral DNA synthesis, and late gene expression in Vero cells. A class of enzymes called DDE recombinases utilize conserved D and E residues to coordinate divalent metal cations in their active sites. We investigated whether the conserved D and E residues in ICP8 were also required for binding metal cations and found that the E1086A D1087A mutant form of ICP8 exhibited altered divalent metal binding in an in vitro iron-induced cleavage assay. These results identify a novel divalent metal cation-binding site in ICP8 that is required for ICP8 functions during viral replication.

  19. Alternative solution model for the ternary carbonate system CaCO3 - MgCO3 - FeCO3 - II. Calibration of a combined ordering model and mixing model

    USGS Publications Warehouse

    McSwiggen, P.L.

    1993-01-01

    Earlier attempts at solution models for the ternary carbonate system have been unable to adequately accommodate the cation ordering which occurs in some of the carbonate phases. The carbonate solution model of this study combines a Margules type of interaction model with a Bragg-Williams type of ordering model. The ordering model determines the equilibrium state of order for a crystal, from which the cation distribution within the lattice can be obtained. The interaction model addresses the effect that mixing different cation species within a given cation layer has on the total free energy of the system. An ordering model was derived, based on the Bragg-Williams approach; it is applicable to ternary systems involving three cations substituting on two sites, and contains three ordering energy parameters (WCaMg, WCaFe, and WCaMgFe). The solution model of this study involves six Margules-type interaction parameters (W12, W21, W13, W31, W23, and W32). Values for the two sets of energy parameters were calculated from experimental data and from compositional relationships in natural assemblages. ?? 1993 Springer-Verlag.

  20. A computational study of anion-modulated cation-π interactions.

    PubMed

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

    2012-05-24

    The interaction of anions with cation-π complexes formed by the guanidinium cation and benzene was thoroughly studied by means of computational methods. Potential energy surface scans were performed in order to evaluate the effect of the anion coming closer to the cation-π pair. Several structures of guanidinium-benzene complexes and anion approaching directions were examined. Supermolecule calculations were performed on ternary complexes formed by guanidinium, benzene, and one anion and the interaction energy was decomposed into its different two- and three-body contributions. The interaction energies were further dissected into their electrostatic, exchange, repulsion, polarization and dispersion contributions by means of local molecular orbital energy decomposition analysis. The results confirm that, besides the electrostatic cation-anion attraction, the effect of the anion over the cation-π interaction is mainly due to polarization and can be rationalized following the changes in the anion-π and the nonadditive (three-body) terms of the interaction. When the cation and the anion are on the same side of the π system, the three-body interaction is anticooperative, but when the anion and the cation are on opposite sides of the π system, the three-body interaction is cooperative. As far as we know, this is the first study where this kind of analysis is carried out with a structured cation as guanidinium with a significant biological interest.

  1. Correlation between cation conduction and ionic morphology in a PEO-based single ion conductor

    NASA Astrophysics Data System (ADS)

    Lin, Kan-Ju; Maranas, Janna

    2011-03-01

    We use molecular dynamics simulation to study ion transport and backbone mobility of a PEO-based single ion conductor. Ion mobility depends on the chemical structure and the local environment of the ions, which consequently impact ionic conductivity. We characterize the aggregation state of the ions, and assess the role of ion complexes in ionomer dynamics. In addition to solvated cations and pairs, higher order ion clusters are found. Most of the ion clusters are in string-like structure and cross-link two or more different ionomer chains through ionic binding. Ionic crosslinks decrease mobility at the ionic co-monomer; hence the mobility of the adjacent PEO segment is influenced. Na ions show slow mobility when they are inside large clusters. The hopping timescale for Na varies from 20 ns to 200. A correlation is found between Na mobility and the number of hops from one coordination site to another. Besides ether oxygens, Na ions in the ionomer also use the anion and the edge of the cluster as hopping sites. The string-like structure of clusters provide less stable sites at the two ends thus ions are more mobile in those regions. We observed Grotthus like mechanism in our ionomer, in which the positive charge migrates within the string-like cluster without the cations actually moving.

  2. Curie temperatures of titanomagnetite in ignimbrites: Effects of emplacement temperatures, cooling rates, exsolution, and cation ordering

    NASA Astrophysics Data System (ADS)

    Jackson, Mike; Bowles, Julie A.

    2014-11-01

    Pumices, ashes, and tuffs from Mt. St. Helens and from Novarupta contain two principal forms of titanomagnetite: homogeneous grains with Curie temperatures in the range 350-500°C and oxyexsolved grains with similar bulk composition, containing ilmenite lamellae and having Curie temperatures above 500°C. Thermomagnetic analyses and isothermal annealing experiments in combination with stratigraphic settings and thermal models show that emplacement temperatures and cooling history may have affected the relative proportions of homogeneous and exsolved grains and have clearly had a strong influence on the Curie temperature of the homogeneous phase. The exsolved grains are most common where emplacement temperatures exceeded 600°C, and in laboratory experiments, heating to over 600°C in air causes the homogeneous titanomagnetites to oxyexsolve rapidly. Where emplacement temperatures were lower, Curie temperatures of the homogeneous grains are systematically related to overburden thickness and cooling timescales, and thermomagnetic curves are generally irreversible, with lower Curie temperatures measured during cooling, but little or no change is observed in room temperature susceptibility. We interpret this irreversible behavior as reflecting variations in the degree of cation ordering in the titanomagnetites, although we cannot conclusively rule out an alternative interpretation involving fine-scale subsolvus unmixing. Short-range ordering within the octahedral sites may play a key role in the observed phenomena. Changes in the Curie temperature have important implications for the acquisition, stabilization, and retention of natural remanence and may in some cases enable quantification of the emplacement temperatures or cooling rates of volcanic units containing homogeneous titanomagnetites.

  3. Effects of cation ordering on the elastic and electronic properties of Mg-Fe silicate phases at high pressures

    NASA Astrophysics Data System (ADS)

    Das, Pratik Kr.; Mandal, Nibir; Arya, A.

    2017-12-01

    Olivine [(Mg, Fe)2SiO4] and pyroxene [(Mg, Fe)Si2O6] are naturally occurring silicate phases. Both the phases crystallize with orthorhombic symmetry, displaying ordering of Mg2+ and Fe2+ in their non-equivalent octahedral lattice sites (M1, M2). We address two major issues: (1) how far an inversion of the cation ordering: type I (Mg2+ in M1; Fe2+ in M2) to type II (Mg2+ in M2; Fe2+in M1) can modify their elastic properties and (2) what are the effects of this inversion on their electronic properties? Using density functional theory, we calculate the elastic constant tensors (Cij) as a function of hydrostatic pressure for types I and II ordering. Our calculations suggest that the inversion (types I to II) in olivine significantly reduces the shear elastic constant C55 (˜25%). This has little effect on the Cij of pyroxene in ambient condition, but the effects become strong at elevated pressures (100 GPa), resulting in large variations (>40%) of all the shear elastic constants: C44, C55, and C66. We predict contrasting variations in compressional (VP) and shear (VS) wave velocities by 1% and 9% and by 2% and 11% for olivine and pyroxene, respectively, on types I to II switchover. Our Debye temperature (θD) calculations show that θD of olivine is less sensitive to ordering inversion, whereas that of pyroxene varies substantially (˜22%) under ambient condition. We evaluate the electronic DOS of pyroxene, and obtain a large difference in the magnetic moment between types I and II.

  4. Aspartic acid 397 in subunit B of the Na+-pumping NADH:quinone oxidoreductase from Vibrio cholerae forms part of a sodium-binding site, is involved in cation selectivity, and affects cation-binding site cooperativity.

    PubMed

    Shea, Michael E; Juárez, Oscar; Cho, Jonathan; Barquera, Blanca

    2013-10-25

    The Na(+)-pumping NADH:quinone complex is found in Vibrio cholerae and other marine and pathogenic bacteria. NADH:ubiquinone oxidoreductase oxidizes NADH and reduces ubiquinone, using the free energy released by this reaction to pump sodium ions across the cell membrane. In a previous report, a conserved aspartic acid residue in the NqrB subunit at position 397, located in the cytosolic face of this protein, was proposed to be involved in the capture of sodium. Here, we studied the role of this residue through the characterization of mutant enzymes in which this aspartic acid was substituted by other residues that change charge and size, such as arginine, serine, lysine, glutamic acid, and cysteine. Our results indicate that NqrB-Asp-397 forms part of one of the at least two sodium-binding sites and that both size and charge at this position are critical for the function of the enzyme. Moreover, we demonstrate that this residue is involved in cation selectivity, has a critical role in the communication between sodium-binding sites, by promoting cooperativity, and controls the electron transfer step involved in sodium uptake (2Fe-2S → FMNC).

  5. Aspartic Acid 397 in Subunit B of the Na+-pumping NADH:Quinone Oxidoreductase from Vibrio cholerae Forms Part of a Sodium-binding Site, Is Involved in Cation Selectivity, and Affects Cation-binding Site Cooperativity

    PubMed Central

    Shea, Michael E.; Juárez, Oscar; Cho, Jonathan; Barquera, Blanca

    2013-01-01

    The Na+-pumping NADH:quinone complex is found in Vibrio cholerae and other marine and pathogenic bacteria. NADH:ubiquinone oxidoreductase oxidizes NADH and reduces ubiquinone, using the free energy released by this reaction to pump sodium ions across the cell membrane. In a previous report, a conserved aspartic acid residue in the NqrB subunit at position 397, located in the cytosolic face of this protein, was proposed to be involved in the capture of sodium. Here, we studied the role of this residue through the characterization of mutant enzymes in which this aspartic acid was substituted by other residues that change charge and size, such as arginine, serine, lysine, glutamic acid, and cysteine. Our results indicate that NqrB-Asp-397 forms part of one of the at least two sodium-binding sites and that both size and charge at this position are critical for the function of the enzyme. Moreover, we demonstrate that this residue is involved in cation selectivity, has a critical role in the communication between sodium-binding sites, by promoting cooperativity, and controls the electron transfer step involved in sodium uptake (2Fe-2S → FMNC). PMID:24030824

  6. Ammonia-water cation and ammonia dimer cation.

    PubMed

    Kim, Hahn; Lee, Han Myoung

    2009-06-25

    We have investigated the structure, interaction energy, electronic properties, and IR spectra of the ammonia-water cation (NH(3)H(2)O)(+) using density functional theory (DFT) and high-level ab initio theory. The ammonia-water cation has three minimum-energy structures of (a) H(2)NH(+)...OH(2), (b) H(3)N(+)...OH(2), and (c) H(3)NH(+)...OH. The lowest-energy structure is (a), followed by (c) and (b). The ammonia dimer cation has two minimum-energy structures [the lowest H(3)NH(+)...NH(2) structure and the second lowest (H(3)N...NH(3))(+) structure]. The minimum transition barrier for the interconversion between (a), (b), and (c) is approximately 6 kcal/mol. Most DFT calculations with various functionals, except a few cases, overstabilize the N...O and N...N binding, predicting different structures from Moller-Plesset second-order perturbation (MP2) theory and the most reliable complete basis set (CBS) limit of coupled cluster theory with single, double, and perturbative triple excitations [CCSD(T)]. Thus, the validity test of the DFT functionals for these ionized molecular systems would be of importance.

  7. Two-dimensional La2/3Sr4/3MnO4 Manganite Films Probed by Epitaxial Strain and Cation Ordering

    NASA Astrophysics Data System (ADS)

    Nelson-Cheeseman, Brittany; Santos, Tiffany; Bhattacharya, Anand

    2010-03-01

    Dimensionality is known to play a central role in the properties of strongly correlated systems. Here we investigate magnetism and transport in thin films of the Ruddlesden-Popper n=1 phase, La1-xSr1+xMnO4. Within this material, the MnO6-octahedra form two-dimensional perovskite sheets separated by an extra rocksalt layer. By fabricating high quality thin films with ozone-assisted molecular beam epitaxy, we study how the effects of epitaxial strain and intentional cation ordering, known as digital synthesis, influence the properties of this 2-dimensional manganite. For example, at the same Mn^3+:Mn^4+ ratio (2:1) as its fully spin-polarized 3D manganite counterpart, this two dimensional analog at x=1/3 only displays a spin glass phase below 20K in bulk. This is believed to result from a competition between superexchange and double exchange, as well as disordered Jahn-Teller distortions. However, in our films we find weak ferromagnetic order up to much higher temperatures in addition to a low temperature spin glass phase. We will discuss how strain and cation order effect the presence of this weak ferromagnetism.

  8. Enhanced Mixed Electronic-Ionic Conductors through Cation Ordering

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

    Jacobson, Allan J.; Morgan, Dane; Grey, Clare

    2014-08-31

    The performance of many energy conversion and storage devices depend on the properties of mixed ionic-electronic conducting (miec) materials. Mixed or ambipolar conductors simultaneously transport ions and electrons and provide the critical interface between chemical and electrical energy in devices such as fuel cells, ion transport membranes, and batteries. Enhancements in storage capacity, reversibility, power density and device lifetime all require new materials and a better understanding of the fundamentals of ambipolar conductivity and surface reactivity.The high temperature properties of the ordered perovksites AA’B 2O 5+x, where A = rare earth ion, Y and B = Ba, Sr were studied.more » The work was motivated by the high oxygen transport and surface exchange rates observed for members of this class of mixed ionic and electronic conductors. A combined experimental and computational approach, including structural, electrochemical, and transport characterization and modeling was used. The approach attacks the problem simultaneously at global (e.g., neutron diffraction and impedance spectroscopy), local (e.g., pair distribution function, nuclear magnetic resonance) and molecular (ab initio thermokinetic modeling) length scales. The objectives of the work were to understand how the cation and associated anion order lead to exceptional ionic and electronic transport properties and surface reactivity in AA’B2O5+x perovskites. A variety of compounds were studied by X-ray and neutron diffraction, measurements of thermodynamics and transport and theoretically. These included PrBaCo 2O 5+x and NdBaCo 2O 5+x, PrBaCo 2-xFexO 6- δ (x = 0, 0.5, 1.0, 1.5 and 2) and LnBaCoFeO 6- δ (Ln = La, Pr, Nd, Sm, Eu and Gd), Sr 3YCo 4O 10.5, YBaMn 2O 5+x. A 0.5A’ 0.5BO 3 (where A=Y, Sc, La, Ce, Pr, Nd, Pm, Sm; A’= Sr, Ba; and B= Fe, Co, Mn, Ni), Ba 2In 2O 5, and La 1 xSr xCoO 3-δ /(La 1-ySry) 2CoO 4±δ interfaces.« less

  9. Frustration relieved ferrimagnetism in novel A- and B-site-ordered quadruple perovskite.

    PubMed

    Chen, Wei-tin; Mizumaki, Masaichiro; Saito, Takashi; Shimakawa, Yuichi

    2013-07-28

    A novel A- and B-site-ordered quadruple perovskite CaCu3Fe2Sb2O12 was obtained and it shows ferrimagnetism below about 170 K. The B-site Fe spin sublattice adapts a tetrahedral framework in a cubic structure and the Fe(3+)-Fe(3+) antiferromagnetic interaction can result in a geometrical spin frustration as seen in a simple perovskite Ca2FeSbO6. With the introduction of Cu(2+) into the A' site, the antiferromagnetic spin frustration is relieved by the strong Cu(2+)-Fe(3+) interaction, and a ferrimagnetic ordering appears at a much higher temperature than the spin-glass transition temperature.

  10. XMCD and Magnetic Evidence for Cation Reordering in Synthetic Mg- and Al-substituted Titanomagnetites

    NASA Astrophysics Data System (ADS)

    Lappe, S. C. L. L.; Bowles, J.; Jackson, M.; Keavney, D.

    2014-12-01

    The titanomagnetite (TM) solid solution (Fe3-xTixO4, 0 ≤ x ≤ 1) is one of the most important natural magnetic minerals used in paleomagnetic studies. Natural TMs with Mg- and Al-substitution have recently been shown to have Curie temperatures (TC) that vary strongly with thermal history, and these variations have been indirectly linked to cation reordering in the crystal lattice (Bowles et al. 2013). Here we present the first direct evidence for cation reordering linked to these TC variations. We have synthesized TMs with varying degrees of Mg2+ and Al3+ substitution to better understand the mechanism at work in the natural samples. TC was determined by measuring magnetic susceptibility as function of temperature under Argon atmosphere. Isothermal annealing experiments between 10-1 to 103 h at temperatures between 300-500°C were conducted. Subsequent TC measurements showed that TC on warming increases for longer anneal times and higher anneal temperatures, whereas TC on cooling decreases. These resulting TC changes can be linked to cation ordering within the crystal structure. Splits of the same samples were studied via X-ray magnetic circular dichroism (XMCD), which is sensitive to both Fe valence state and site occupancy. Preliminary results suggest differences in Fe2+/Fe3+ site occupancy for samples of different compositions for different annealing treatments. Using the data collected for these synthetic samples we hope to gain further insight into the complex relationship between thermal history and cation distribution leading to changes in TC. So far, our understanding of the acquisition of thermal remanent magnetization (TRM) in TMs is predicated on the assumption that TC is a constant only depending on the mineral composition. However, the distribution of the magnetic Fe2+ and Fe3+ cations within the crystal lattice has a strong influence on the value of TC and cation (dis-)/ordering processes can result in large changes in TC. In natural samples

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

    PubMed

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

    2012-12-01

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

  12. Use of Order Sets in Inpatient Computerized Provider Order Entry Systems: A Comparative Analysis of Usage Patterns at Seven Sites

    PubMed Central

    Wright, Adam; Feblowitz, Joshua C.; Pang, Justine E.; Carpenter, James D.; Krall, Michael A.; Middleton, Blackford; Sittig, Dean F.

    2012-01-01

    Background Many computerized provider order entry (CPOE) systems include the ability to create electronic order sets: collections of clinically-related orders grouped by purpose. Order sets promise to make CPOE systems more efficient, improve care quality and increase adherence to evidence-based guidelines. However, the development and implementation of order sets can be expensive and time-consuming and limited literature exists about their utilization. Methods Based on analysis of order set usage logs from a diverse purposive sample of seven sites with commercially- and internally-developed inpatient CPOE systems, we developed an original order set classification system. Order sets were categorized across seven non-mutually exclusive axes: admission/discharge/transfer (ADT), perioperative, condition-specific, task-specific, service-specific, convenience, and personal. In addition, 731 unique subtypes were identified within five axes: four in ADT (S=4), three in perioperative, 144 in condition-specific, 513 in task-specific, and 67 in service-specific. Results Order sets (n=1,914) were used a total of 676,142 times at the participating sites during a one-year period. ADT and perioperative order sets accounted for 27.6% and 24.2% of usage respectively. Peripartum/labor, chest pain/Acute Coronary Syndrome/Myocardial Infarction and diabetes order sets accounted for 51.6% of condition-specific usage. Insulin, angiography/angioplasty and arthroplasty order sets accounted for 19.4% of task-specific usage. Emergency/trauma, Obstetrics/Gynecology/Labor Delivery and anesthesia accounted for 32.4% of service-specific usage. Overall, the top 20% of order sets accounted for 90.1% of all usage. Additional salient patterns are identified and described. Conclusion We observed recurrent patterns in order set usage across multiple sites as well as meaningful variations between sites. Vendors and institutional developers should identify high-value order set types through concrete

  13. Monovalent Cation Activation of the Radical SAM Enzyme Pyruvate Formate-Lyase Activating Enzyme.

    PubMed

    Shisler, Krista A; Hutcheson, Rachel U; Horitani, Masaki; Duschene, Kaitlin S; Crain, Adam V; Byer, Amanda S; Shepard, Eric M; Rasmussen, Ashley; Yang, Jian; Broderick, William E; Vey, Jessica L; Drennan, Catherine L; Hoffman, Brian M; Broderick, Joan B

    2017-08-30

    Pyruvate formate-lyase activating enzyme (PFL-AE) is a radical S-adenosyl-l-methionine (SAM) enzyme that installs a catalytically essential glycyl radical on pyruvate formate-lyase. We show that PFL-AE binds a catalytically essential monovalent cation at its active site, yet another parallel with B 12 enzymes, and we characterize this cation site by a combination of structural, biochemical, and spectroscopic approaches. Refinement of the PFL-AE crystal structure reveals Na + as the most likely ion present in the solved structures, and pulsed electron nuclear double resonance (ENDOR) demonstrates that the same cation site is occupied by 23 Na in the solution state of the as-isolated enzyme. A SAM carboxylate-oxygen is an M + ligand, and EPR and circular dichroism spectroscopies reveal that both the site occupancy and the identity of the cation perturb the electronic properties of the SAM-chelated iron-sulfur cluster. ENDOR studies of the PFL-AE/[ 13 C-methyl]-SAM complex show that the target sulfonium positioning varies with the cation, while the observation of an isotropic hyperfine coupling to the cation by ENDOR measurements establishes its intimate, SAM-mediated interaction with the cluster. This monovalent cation site controls enzyme activity: (i) PFL-AE in the absence of any simple monovalent cations has little-no activity; and (ii) among monocations, going down Group 1 of the periodic table from Li + to Cs + , PFL-AE activity sharply maximizes at K + , with NH 4 + closely matching the efficacy of K + . PFL-AE is thus a type I M + -activated enzyme whose M + controls reactivity by interactions with the cosubstrate, SAM, which is bound to the catalytic iron-sulfur cluster.

  14. Antiferromagnetic interaction between A'-site Mn spins in A-site-ordered perovskite YMn3Al4O12.

    PubMed

    Tohyama, Takenori; Saito, Takashi; Mizumaki, Masaichiro; Agui, Akane; Shimakawa, Yuichi

    2010-03-01

    The A-site-ordered perovskite YMn(3)Al(4)O(12) was prepared by high-pressure synthesis. Structural analysis with synchrotron powder X-ray diffraction data and the Mn L-edges X-ray absorption spectrum revealed that the compound has a chemical composition Y(3+)Mn(3+)(3)Al(3+)(4)O(2-)(12) with magnetic Mn(3+) at the A' site and non-magnetic Al(3+) at the B site. An antiferromagnetic interaction between the A'-site Mn(3+) spins is induced by the nearest neighboring Mn-Mn direct exchange interaction and causes an antiferromagnetic transition at 34.3 K.

  15. An uptake of cationized ferritin by alveolar type I cells in airway-instilled goat lung: distribution of anionic sites on the epithelial surface.

    PubMed

    Atwal, O S; Viel, L; Minhas, K J

    1990-07-01

    The present study has investigated ultrastructural localization of anionic sites on the luminal surface of the alveolar epithelium of goat lung by direct airway instillation of cationized ferritin (CF) in the cranial lobe of the right lung through a bronchoscope. The cationic probe decorated preferentially the luminal plasmalemmal vesicles and plasmalemma proper of alveolar type I cell. This indicated the presence of highly charged anionic microdomains at these binding sites. The ligand was internalized in the free plasmalemmal vesicles of alveolar type I cell within 2 min. Heavy decoration of vesicles at 5 min of perfusion indicated that the amount of CF internalization increased with its concentration in the alveoli. It is suggested that exposure of alveolar surface to several gases of ruminal-origin induces changes in the surface charge of luminal plasmalemma of alveolar type I cells. The significance of these anionic plasmalemmal sites is discussed in relation to the adjustment of osmotic pressure gradient across the alveolar-capillary membrane of the ruminant lung.

  16. Fragmentation of alpha-Radical Cations of Arginine-Containing Peptides

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

    Laskin, Julia; Yang, Zhibo; Ng, Dominic C.

    2010-04-01

    Fragmentation pathways of peptide radical cations, M+, with well-defined initial location of the radical site were explored using collision-induced dissociation (CID) experiments. Peptide radical cations were produced by gas-phase fragmentation of CoIII(salen)-peptide complexes [salen = N,N´-ethylenebis (salicylideneaminato)]. Subsequent hydrogen abstraction from the -carbon of the side chain followed by Ca-C bond cleavage results in the loss of a neutral side chain and formation of an a-radical cation with the radical site localized on the a-carbon of the backbone. Similar CID spectra dominated by radical-driven dissociation products were obtained for a number of a-radicals when the basic arginine side chain wasmore » present in the sequence. In contrast, proton-driven fragmentation dominates CID spectra of a-radicals produced via the loss of the arginine side chain. Our results suggest that in most cases radical migration precedes fragmentation of large peptide radical cations.« less

  17. The Role and Specificity of the Catalytic and Regulatory Cation-binding Sites of the Na+-pumping NADH:Quinone Oxidoreductase from Vibrio cholerae*

    PubMed Central

    Juárez, Oscar; Shea, Michael E.; Makhatadze, George I.; Barquera, Blanca

    2011-01-01

    The Na+-translocating NADH:quinone oxidoreductase is the entry site for electrons into the respiratory chain and the main sodium pump in Vibrio cholerae and many other pathogenic bacteria. In this work, we have employed steady-state and transient kinetics, together with equilibrium binding measurements to define the number of cation-binding sites and characterize their roles in the enzyme. Our results show that sodium and lithium ions stimulate enzyme activity, and that Na+-NQR enables pumping of Li+, as well as Na+ across the membrane. We also confirm that the enzyme is not able to translocate other monovalent cations, such as potassium or rubidium. Although potassium is not used as a substrate, Na+-NQR contains a regulatory site for this ion, which acts as a nonessential activator, increasing the activity and affinity for sodium. Rubidium can bind to the same site as potassium, but instead of being activated, enzyme turnover is inhibited. Activity measurements in the presence of both sodium and lithium indicate that the enzyme contains at least two functional sodium-binding sites. We also show that the binding sites are not exclusively responsible for ion selectivity, and other steps downstream in the mechanism also play a role. Finally, equilibrium-binding measurements with 22Na+ show that, in both its oxidized and reduced states, Na+-NQR binds three sodium ions, and that the affinity for sodium is the same for both of these states. PMID:21652714

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

    PubMed

    Fink, Krzysztof; Boratyński, Janusz

    2014-11-07

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

  19. Solubility of polyvalent cations in fogwater at an urban site in Strasbourg (France)

    NASA Astrophysics Data System (ADS)

    Millet, M.; Wortham, H.; Mirabel, Ph.

    The concentrations in the soluble and total (soluble + insoluble) fractions of Mg, Ca, Fe, Mn, Zn, Al, Cd and Pb have been analysed by "inductively coupled plasma (ICP)" in 14 fog events collected in 1992 at an urban site in France (Strasbourg). For each fog event, two droplet size categories (2-6 μm and 5-8 μm) have been collected separately. For the analysis of the polyvalent cations in the soluble and total fractions, an analytical procedure using ICP and filtration on cellulose/PVC filters has been developed. The study of the solubility of some polyvalent cations has shown that two of the most important factors controlling the partitioning between the soluble and insoluble fraction are the nature of the particles and the pH of the fogwater. The influence of pH depended on the element. The solubility of Pb, Cd, Al, Fe, Mg, and Ca were pH dependent whereas, Zn and Mn solubility varied but no relationship with pH existed, ranging between 25 and 100% and 10 and 100%, respectively. On the other hand, Mg, Pb and Ca were predominantly present in the soluble phase, whereas Al was prevalent in the insoluble fraction. In the case of Cd and Fe., the presence in the soluble or insoluble phase depended largely on the fogwater pH.

  20. Negative Oxygen Isotope Effect in Manganites with an Ordered Cation Arrangement in a High Magnetic Field

    NASA Astrophysics Data System (ADS)

    Taldenkov, A. N.; Snegirev, V. V.; Babushkina, N. A.; Kalitka, V. S.; Kaul', A. R.

    2018-03-01

    The oxygen isotope effect in PrBaMn2 16-18 O5.97 manganite with an ordered cation arrangement is studied. The field dependences of magnetic susceptibility and magnetization are measured in the temperature range 100-270 K and magnetic fields up to 32 T. A significant increase in the temperature of the spin-reorientation antiferromagnet-ferromagnet phase transition is detected in samples enriched in heavy oxygen 18O (negative isotope effect). The transition temperature and the isotope effect depend strongly on the magnetic field. An H-T phase diagram is plotted for samples with various isotope compositions. An analysis of the experimental results demonstrates that the detected negative isotope effect and the giant positive isotope effect revealed earlier in doped manganites have the same nature. The mechanisms of appearance of isotope effects are discussed in terms of the double exchange model under a polaron narrowing of the free carrier band.

  1. Alternative solution model for the ternary carbonate system CaCO3 - MgCO3 - FeCO3 - I. A ternary Bragg-Williams ordering model

    USGS Publications Warehouse

    McSwiggen, P.L.

    1993-01-01

    The minerals of the ternary carbonate system CaCO3 - MgCO3 - FeCO3 represent a complex series of solid solutions and ordering states. An understanding of those complexities requires a solution model that can both duplicate the subsolidus phase relationships and generate correct values for the activities. Such a solution model must account for the changes in the total energy of the system resulting from a change in the ordering state of the individual constituents. Various ordering models have been applied to binary carbonate systems, but no attempts have previously been made to model the ordering in the ternary system. This study derives a new set of equations that allow for the equilibrium degree of order to be calculated for a system involving three cations mixing on two sites, as in the case of the ternary carbonates. The method is based on the Bragg-Williams approach. From the degree of order, the mole fractions of the three cations in each of the two sites can be determined. Once the site occupancies have been established, a Margules-type mixing model can be used to determine the free energy of mixing in the solid solution and therefore the activities of the various components. ?? 1993 Springer-Verlag.

  2. Electronic and Electrochemical Properties of Li 1–x Mn 1.5 Ni 0.5 O 4 Spinel Cathodes As a Function of Lithium Content and Cation Ordering

    DOE PAGES

    Moorhead-Rosenberg, Zach; Huq, Ashfia; Goodenough, John B.; ...

    2015-10-05

    The electronic and electrochemical properties of the high-voltage spinel LiMn 1.5Ni 0.5O 4 as a function of cation ordering and lithium content have been investigated. Conductivity and activation energy measurements confirm that charge transfer occurs by small polaron hopping and the charge carrier conduction is easier in the Ni:3d band than in the in Mn:3d band. Seebeck coefficient data reveal that the Ni 2+/ 3+. and Ni 3+/ 4+ redox couples are combined in a single,3d band, and that maximum charge carrier concentration occurs where the average Ni oxidation state is close to 3+, corresponding to x = 0.5 inmore » Li Li 1-xMn 1.5Ni 0.5O 4. Furthermore, maximum electronic conductivity is found at x = 0.5, regardless of cation ordering. The thermodynamically stable phases formed during cycling were investigated by recording the X-ray diffraction (XRD) of chemically delithiated powders. The more ordered spinels maintained two separate two-phase regions upon lithium extraction, while the more disordered samples exhibited a solid-solubility region from LiMn 1.5Ni 0.5O 4 to Li 0.5Mn 1.5Ni 0.5O 4. The conductivity and phase-transformation data of four samples with varying degrees of cation ordering were compared to the electrochemical data collected with lithium cells. Only the most ordered spinel showed inferior rate performance, while the sample annealed for a shorter time performed comparable to the unannealed or disordered samples. Our results challenge the most common beliefs about high-voltage spinel: (i) low Mn 3+ content is responsible for poor rate performance and (ii) thermodynamically stable solid-solubility is critical for fast kinetics.« less

  3. Multicolor fluorescence of a styrylquinoline dye tuned by metal cations.

    PubMed

    Shiraishi, Yasuhiro; Ichimura, Chizuru; Sumiya, Shigehiro; Hirai, Takayuki

    2011-07-18

    A styrylquinoline dye with a dipicolylamine (DPA) moiety (1) has been synthesized. The dye 1 in acetonitrile demonstrates multicolor fluorescence upon addition of different metal cations. Compound 1 shows a green fluorescence without cations. Coordination of 1 with Cd(2+) shows a blue emission, while with Hg(2+) and Pb(2+) exhibits yellow and orange emissions, respectively. The different fluorescence spectra are due to the change in intramolecular charge transfer (ICT) properties of 1 upon coordination with different cations. The DPA and quinoline moieties of 1 behave as the electron donor and acceptor units, respectively, and both units act as the coordination site for metal cations. Cd(2+) coordinates with the DPA unit. This reduces the donor ability of the unit and decreases the energy level of HOMO. This results in an increase in HOMO-LUMO gap and blue shifts the emission. Hg(2+) or Pb(2+) coordinate with both DPA and quinoline units. The coordination with the quinoline unit decreases the energy level of LUMO. This results in a decrease in HOMO-LUMO gap and red shifts the emission. Addition of two different metal cations successfully creates intermediate colors; in particular, the addition of Cd(2+) and Pb(2+) at once creates a bright white fluorescence. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Cation Exchange in the Presence of Oil in Porous Media

    PubMed Central

    2017-01-01

    Cation exchange is an interfacial process during which cations on a clay surface are replaced by other cations. This study investigates the effect of oil type and composition on cation exchange on rock surfaces, relevant for a variety of oil-recovery processes. We perform experiments in which brine with a different composition than that of the in situ brine is injected into cores with and without remaining oil saturation. The cation-exchange capacity (CEC) of the rocks was calculated using PHREEQC software (coupled to a multipurpose transport simulator) with the ionic composition of the effluent histories as input parameters. We observe that in the presence of crude oil, ion exchange is a kinetically controlled process and its rate depends on residence time of the oil in the pore, the temperature, and kinetic rate of adsorption of the polar groups on the rock surface. The cation-exchange process occurs in two stages during two phase flow in porous media. Initially, the charged sites of the internal surface of the clays establish a new equilibrium by exchanging cations with the aqueous phase. At later stages, the components of the aqueous and oleic phases compete for the charged sites on the external surface or edges of the clays. When there is sufficient time for crude oil to interact with the rock (i.e., when the core is aged with crude oil), a fraction of the charged sites are neutralized by the charged components stemming from crude oil. Moreover, the positively charged calcite and dolomite surfaces (at the prevailing pH environment of our experiments) are covered with the negatively charged components of the crude oil and therefore less mineral dissolution takes place when oil is present in porous media. PMID:28580442

  5. Comparative study of A-site order in the lead-free bismuth titanates M{sub 1/2}Bi{sub 1/2}TiO{sub 3} (M=Li, Na, K, Rb, Cs, Ag, Tl) from first-principles

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

    Gröting, Melanie, E-mail: groeting@mm.tu-darmstadt.de; Albe, Karsten, E-mail: albe@mm.tu-darmstadt.de

    2014-05-01

    We investigate the possibility of enhancing chemical order in the relaxor ferroelectric Na{sub 1/2}Bi{sub 1/2}TiO{sub 3} upon substitution of Na{sup +} by other monovalent cations M{sup +} using total energy calculations based on density functional theory. All chemically available monovalent cations M{sup +}, which are Li, Na, Ag, K, Tl, Rb and Cs, are considered and an analysis of the structurally relaxed structures in terms of symmetry-adapted distortion modes is given in order to quantify the chemically induced structural distortions. We demonstrate that the replacement of Na{sup +} by other monovalent cations can hardly alter the tendency of chemical ordermore » with respect to Na{sub 1/2}Bi{sub 1/2}TiO{sub 3}. Only Tl{sub 1/2}Bi{sub 1/2}TiO{sub 3} and Ag{sub 1/2}Bi{sub 1/2}TiO{sub 3} show enhanced tendency for chemical ordering. Both heavy metals behave similar to the light alkali metals in terms of structural relaxations and relative stabilities of the ordered configurations. Although a comparison of the Goldschmidt factors of components (M TiO{sub 3}){sup −} reveals for Tl a value above the upper stability limit for perovskites, the additional lone-pair effect of Tl{sup +} stabilizes the ordered structure. - Graphical abstract: Amplitudes of chemically induced distortion modes in different ordered perovskites M{sub 1/2}Bi{sub 1/2}TiO{sub 3} and visualisation of atomic displacements associated with distortion mode X{sup +}{sub 1} in the 001-ordered compounds Li{sub 1/2}Bi{sub 1/2}TiO{sub 3} and Cs{sub 1/2}Bi{sub 1/2}TiO{sub 3}. Due to a substantial size mismatch between bismuth (green) and caesium (dark blue), incorporation of the latter leads to enhanced displacements of oxygen atoms (red) and suppresses displacements of titanium (silver) as compared to lithium (light blue) or other smaller monovalent cations. - Highlights: • Lead-free A-site mixed bismuth titanates M{sub 1/2}Bi{sub 1/2}TiO{sub 3} are studied by first-principles calculations.

  6. The role of the anionic and cationic pt sites in the adsorption site preference of water and ethanol on defected Pt4/Pt(111) substrates: A density functional theory investigation within the D3 van der waals corrections

    NASA Astrophysics Data System (ADS)

    Seminovski, Yohanna; Amaral, Rafael C.; Tereshchuk, Polina; Da Silva, Juarez L. F.

    2018-01-01

    Platinum (Pt) atoms in the bulk face-centered cubic structure have neutral charge because they are equivalent by symmetry, however, in clean Pt surfaces, the effective charge on Pt atoms can turn slightly negative (anionic) or positive (cationic) while increasing substantially in magnitude for defected (low-coordinated) Pt sites. The effective charge affect the adsorption properties of molecular species on Pt surfaces and it can compete in importance with the coupling of the substrate-molecule electronic states. Although several studies have been reported due to the importance of Pt for catalysis, our understanding of the role played by low-coordinated sites is still limited. Here, we employ density functional theory within the Perdew-Burke-Ernzerhof exchange-correlation functional and the D3 van der Waals (vdW) correction to investigate the role of the cationic and anionic Pt sites on the adsorption properties of ethanol and water on defected Pt4/Pt(111) substrates. Four substrates were carefully selected, namely, two two-dimensional (2D) Pt4 configurations (2D-strand and 2D-island) and two tri-dimensional (3D) Pt4 (3D-fcc and 3D-hcp), to understand the role of coordination, effective charge, and coupling of the electronic states in the adsorption properties. From the Bader charge analysis, we identified the cationic and anionic sites among the Pt atoms exposed to the vacuum region in the Pt4/Pt(111) substrates. We found that ethanol and water bind via the anionic O atoms to the low-coordinated defected Pt sites of the substrates, where the angle PtOH is nearly 100° for most configurations. In the 3D-fcc or 3D-hcp defected configurations, the lowest-coordinated Pt atoms are anionic, hence, those Pt sites are not preferable for the adsorption of O atoms. The charge transfer from water and ethanol to the Pt substrates has similar magnitude for all cases, which implies similar Coulomb contribution to the adsorption energy. Moreover, we found a correlation of the

  7. Site identity and importance in cosubstituted bixbyite In 2O 3

    DOE PAGES

    Rickert, Karl; Harris, Jeremy; Sedefoglu, Nazmi; ...

    2017-02-09

    The bixbyite structure of In 2O 3 has two nonequivalent, 6-coordinate cation sites and, when Sn is doped into In 2O 3, the Sn prefers the “b-site” and produces a highly conductive material. When divalent/tetravalent cation pairs are cosubstituted into In 2O 3, however, the conductivity increases to a lesser extent and the site occupancy is less understood. We examine the site occupancy in the Mg xIn 2–2xSn xO 3 and Zn xIn 2–2xSn xO 3 systems with high resolution X-ray and neutron diffraction and density functional theory computations, respectively. In these sample cases and those that are previously reportedmore » in the M xIn 2–2xSn xO 3 (M = Cu, Ni, or Zn) systems, the solubility limit is greater than 25%, ensuring that the b-site cannot be the exclusively preferred site as it is in Sn:In 2O 3. Prior to this saturation point, we report that the M 2+ cation always has at least a partial occupancy on the d-site and the Sn 4+ cation has at least a partial occupancy on the b-site. The energies of formation for these configurations are highly favored, and prefer that the divalent and tetravalent substitutes are adjacent in the crystal lattice, which suggests short range ordering. Diffuse reflectance and 4-point probe measurements of Mg xIn 2–xSn xO 3 demonstrate that it can maintain an optical band gap >2.8 eV while surpassing 1000 S/cm in conductivity. Furthermore, understanding how multiple constituents occupy the two nonequivalent cation sites can provide information on how to optimize cosubstituted systems to increase Sn solubility while maintaining its dopant nature, achieving maximum conductivity.« less

  8. Site identity and importance in cosubstituted bixbyite In 2O 3

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

    Rickert, Karl; Harris, Jeremy; Sedefoglu, Nazmi

    The bixbyite structure of In 2O 3 has two nonequivalent, 6-coordinate cation sites and, when Sn is doped into In 2O 3, the Sn prefers the “b-site” and produces a highly conductive material. When divalent/tetravalent cation pairs are cosubstituted into In 2O 3, however, the conductivity increases to a lesser extent and the site occupancy is less understood. We examine the site occupancy in the Mg xIn 2–2xSn xO 3 and Zn xIn 2–2xSn xO 3 systems with high resolution X-ray and neutron diffraction and density functional theory computations, respectively. In these sample cases and those that are previously reportedmore » in the M xIn 2–2xSn xO 3 (M = Cu, Ni, or Zn) systems, the solubility limit is greater than 25%, ensuring that the b-site cannot be the exclusively preferred site as it is in Sn:In 2O 3. Prior to this saturation point, we report that the M 2+ cation always has at least a partial occupancy on the d-site and the Sn 4+ cation has at least a partial occupancy on the b-site. The energies of formation for these configurations are highly favored, and prefer that the divalent and tetravalent substitutes are adjacent in the crystal lattice, which suggests short range ordering. Diffuse reflectance and 4-point probe measurements of Mg xIn 2–xSn xO 3 demonstrate that it can maintain an optical band gap >2.8 eV while surpassing 1000 S/cm in conductivity. Furthermore, understanding how multiple constituents occupy the two nonequivalent cation sites can provide information on how to optimize cosubstituted systems to increase Sn solubility while maintaining its dopant nature, achieving maximum conductivity.« less

  9. A Cross-site Qualitative Study of Physician Order Entry

    PubMed Central

    Ash, Joan S.; Gorman, Paul N.; Lavelle, Mary; Payne, Thomas H.; Massaro, Thomas A.; Frantz, Gerri L.; Lyman, Jason A.

    2003-01-01

    Objective: To describe the perceptions of diverse professionals involved in computerized physician order entry (POE) at sites where POE has been successfully implemented and to identify differences between teaching and nonteaching hospitals. Design: A multidisciplinary team used observation, focus groups, and interviews with clinical, administrative, and information technology staff to gather data at three sites. Field notes and transcripts were coded using an inductive approach to identify patterns and themes in the data. Measurements: Patterns and themes concerning perceptions of POE were identified. Results: Four high-level themes were identified: (1) organizational issues such as collaboration, pride, culture, power, politics, and control; (2) clinical and professional issues involving adaptation to local practices, preferences, and policies; (3) technical/implementation issues, including usability, time, training and support; and (4) issues related to the organization of information and knowledge, such as system rigidity and integration. Relevant differences between teaching and nonteaching hospitals include extent of collaboration, staff longevity, and organizational missions. Conclusion: An organizational culture characterized by collaboration and trust and an ongoing process that includes active clinician engagement in adaptation of the technology were important elements in successful implementation of physician order entry at the institutions that we studied. PMID:12595408

  10. Cation ordering in orthopyroxenes and cooling rates of meteorites: Low temperature cooling rates of Estherville, Bondoc and Shaw

    NASA Technical Reports Server (NTRS)

    Ganguly, J.; Yang, H.; Ghose, S.

    1993-01-01

    The cooling rates of meteorites provide important constraints on the size of their parent bodies, and their accretionary and evolutionary histories. However, the cooling rates obtained so far from the commonly used metallographic, radiometric and fission-track methods have been sometimes quite controversial, such as in the case of the mesosiderites and the meteorite Shaw. We have undertaken a systematic study of the cooling rates of meteorites using a different approach, which involves single crystal x-ray determination of Fe(2+)-Mg ordering in orthopyroxenes (OP(x)) in meteorites, subject to bulk compositional constraints, and numerical simulation of the evolution of the ordering state as a function of cooling rate, within the framework of the thermodynamic and kinetic principles governing cation ordering. We report the results obtained for OP(x) crystals from Shaw and two mesosiderites, Estherville and Bondoc.

  11. Lanthanum-rich fluorbritholite-(Ce) from young alkaline volcanic rock of Eifel (Germany) and its crystal structure. Cation ordering in britholites

    NASA Astrophysics Data System (ADS)

    Zubkova, N. V.; Chukanov, N. V.; Pekov, I. V.; Schäfer, C.; Yapaskurt, V. O.; Pushcharovsky, D. Yu.

    2015-09-01

    Structure (R=0.0213) of lanthanum-rich fluorbritholite (Ce) [(Ce2.47La2.31Nd0.22Pr0.13Y0.07)5.20Ca4.20Th0.27Mn0.19Sr0.09]9.95(Si5.37P0.63)6O24.16F1.95 from sanidinite in Laacher See, Eifel, Germany was studied on a monocrystal. The structure [space group P63/m, a = 9.58949 (13), c = 7.0289 (11) Å, V = 559.770 (14)Å3] is identical to structures of members of apatite supergroup. Relationships of major cations in polyhedra M(1)O9 = (Ca0.6 REE 0.4), and in polyhedral M(2)O6F = ( REE 0.7Ca0.3). Substantial structural order M(1) and M(2) is defined, simplified structural formula: (Ca, LREE)2( LREE,Ca)3(SiO4)3F. Analysis of data on crystal chemistry of britholite was carried out. It was demonstrated that distribution of cations on M(1)and M(2)-positions is always characteristic of partial structural order. Clear tendency of LREE concentration in M(2) position was noted.

  12. Investigation of magnetic ordering and cation distribution in the spinel ferrites CrxFe3-xO4 (0.0≤x≤1.0)

    NASA Astrophysics Data System (ADS)

    Tang, G. D.; Han, Q. J.; Xu, J.; Ji, D. H.; Qi, W. H.; Li, Z. Z.; Shang, Z. F.; Zhang, X. Y.

    2014-04-01

    Ferrite powder samples of CrxFe3-xO4 (0.0≤x≤1.0) were prepared by chemical co-precipitation, and calcined in a tube furnace with argon-flow at 1723 K for 2 h. X-ray diffraction patterns indicated that all the samples had an (A)[B]2O4 single phase cubic spinel structure with a Fd3barm space group. Magnetic measurements indicated that the magnetization of the samples decreased with the Cr doping level. A new model for the magnetic ordering in these samples was employed to explain the dependence of the magnetization and cation distribution on the Cr doping level; namely, taking into consideration constraints arising from Hund's rules and from the spin direction of the itinerant 3d electrons, the directions of the Cr2+ and Cr3+ cation magnetic moments were taken to lie antiparallel to the moments of the Fe cations within the same sub-lattice (A or B sub-lattice).

  13. A novel route to recognizing quaternary ammonium cations using electrospray mass spectrometry.

    PubMed

    Shackman, Holly M; Ding, Wei; Bolgar, Mark S

    2015-01-01

    Characterizing and elucidating structures is a commonplace and necessary activity in the pharmaceutical industry with mass spectrometry and NMR being the primary tools for analysis. Although many functional groups are readily identifiable, quaternary ammonium cations have proven to be difficult to unequivocally identify using these techniques. Due to the lack of an N-H bond, quaternary ammonium groups can only be detected in the (1)H NMR spectra by weak signals generated from long-range (14)N-H coupling, which by themselves are inconclusive evidence of a quaternary ammonium functional group. Due to their low intensity, these signals are frequently not detected. Additionally, ions cannot be differentiated in a mass spectrum as an M(+) or [M + H](+) ion without prior knowledge of the compound's structure. In order to utilize mass spectrometry as a tool for determining this functionality, ion cluster formation of quaternary ammonium cations and non-quaternary amines was studied using electrospray ionization. Several mobile phase modifiers were compared; however, the addition of small amounts of trifluoroacetic acid proved superior in producing characteristic and intense [M +2TFA](-) clusters for compounds containing quaternary ammonium cations when using negative electrospray. By fragmenting this characteristic ion using CID, nearly all compounds studied could be unambiguously identified as containing a quaternary ammonium cation or a non-quaternary amine attributable to the presence (non-quaternary amine) or absence (quaternary ammonium cation) of the resulting [2TFA + H](-) ion in the product spectra. This method of analysis provides a rapid, novel, and reliable technique for indicating the presence of quaternary ammonium cations in order to aid in structural elucidation.

  14. Cation Effects on the Electron-Acceptor Side of Photosystem II.

    PubMed

    Khan, Sahr; Sun, Jennifer S; Brudvig, Gary W

    2015-06-18

    The normal pathway of electron transfer on the electron-acceptor side of photosystem II (PSII) involves electron transfer from quinone A, QA, to quinone B, QB. It is possible to redirect electrons from QA(-) to water-soluble Co(III) complexes, which opens a new avenue for harvesting electrons from water oxidation by immobilization of PSII on electrode surfaces. Herein, the kinetics of electron transfer from QA(-) to [Co(III)(terpy)2](3+) (terpy = 2,2';6',2″-terpyridine) are investigated with a spectrophotometric assay revealing that the reaction follows Michaelis-Menten saturation kinetics, is inhibited by cations, and is not affected by variation of the QA reduction potential. A negatively charged site on the stromal surface of the PSII protein complex, composed of glutamic acid residues near QA, is hypothesized to bind cations, especially divalent cations. The cations are proposed to tune the redox properties of QA through electrostatic interactions. These observations may thus explain the molecular basis of the effect of divalent cations like Ca(2+), Sr(2+), Mg(2+), and Zn(2+) on the redox properties of the quinones in PSII, which has previously been attributed to long-range conformational changes propagated from divalent cations binding to the Ca(II)-binding site in the oxygen-evolving complex on the lumenal side of the PSII complex.

  15. Tree species affect cation exchange capacity (CEC) and cation binding properties of organic matter in acid forest soils.

    PubMed

    Gruba, Piotr; Mulder, Jan

    2015-04-01

    Soil organic matter (SOM) in forest soil is of major importance for cation binding and acid buffering, but its characteristics may differ among soils under different tree species. We investigated acidity, cation exchange properties and Al bonding to SOM in stands of Scots pine, pedunculate oak, Norway spruce, European beech and common hornbeam in southern Poland. The content of total carbon (Ct) was by far the major contributor to total cation exchange capacity (CECt) even in loamy soils and a strong relationship between Ct and CECt was found. The slope of the regression of CECt to Ct increased in the order hornbeam≈oaksites of SOM at any value in the acid pH range was smallest for hornbeam and oak, and largest for spruce and pine soils. This was supported by the apparent dissociation constant (pKapp) values of SOM, which were largest in soils under oak. The maximum values of Al saturation were similar between the stands. However, maximum Al bonding to SOM occurred at higher pH values in soils under pine and spruce than under oak. Therefore, at any value in the acid pH range, the SOM in pine soil has less Al complexed and more adsorbed H+ than SOM from oak soils. Such differences in Al and H bonding are not only important for pH buffering and metal solubility controls, but also for stabilization of SOM via saturation of functional groups by Al and H. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. Cation export by overland flow in a recently burnt forest area in north-central Portugal.

    PubMed

    Machado, A I; Serpa, D; Ferreira, R V; Rodríguez-Blanco, M L; Pinto, R; Nunes, M I; Cerqueira, M A; Keizer, J J

    2015-08-15

    The current fire regime in the Mediterranean Basin constitutes a serious threat to natural ecosystems because it drastically enhances surface runoff and soil erosion in the affected areas. Besides soil particles themselves, soil cations can be lost by fire-enhanced overland flow, increasing the risk of fertility loss of the typically shallow and nutrient poor Mediterranean soils. Although the importance of cations for land-use sustainability is widely recognized, cation losses by post-fire runoff have received little research attention. The present study aimed to address this research gap by assessing total exports of Na(+), K(+), Ca(2+) and Mg(2+) in a recently burnt forest area in north-central Portugal. These exports were compared for two types of planted forest (eucalypt vs. maritime pine plantations), two types of parent materials (schist vs. granite) and for two spatial scales (micro-plot vs. hill slope). The study sites were a eucalypt plantation on granite (BEG), a eucalypt plantation on schist (BES) and a maritime pine plantation on schist (BPS). Overland flow samples were collected during the first six months after the wildfire. Cation losses differed strikingly between the two forest types on schist, being higher at the eucalypt than pine site. This difference was evident at both spatial scales, and probably due to the extensive cover of a needle cast from the scorched pine crowns. The role of parent material in cation export was less straightforward as it varied with spatial scale. Cation losses were higher for the eucalypt plantation on schist than for that on granite at the micro-plot scale, whereas the reverse was observed at the hill slope scale. Finally, cation yields were higher at the micro-plot than slope scale, in agreement with the general notion of scaling-effect in runoff generation. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. Convergent Use of Heptacoordination for Cation Selectivity by RNA and Protein Metalloregulators.

    PubMed

    Bachas, Sharrol T; Ferré-D'Amaré, Adrian R

    2018-05-04

    The large yybP-ykoY family of bacterial riboswitches is broadly distributed phylogenetically. Previously, these gene-regulatory RNAs were proposed to respond to Mn 2+ . X-ray crystallography revealed a binuclear cation-binding pocket. This comprises one hexacoordinate site, with six oxygen ligands, which preorganizes the second, with five oxygen and one nitrogen ligands. The relatively soft nitrogen ligand was proposed to confer affinity for Mn 2+ , but how this excludes other soft cations remained enigmatic. By subjecting representative yybP-ykoY riboswitches to diverse cations in vitro, we now find that these RNAs exhibit limited transition metal ion selectivity. Among the cations tested, Cd 2+ and Mn 2+ bind most tightly, and comparison of three new Cd 2+ -bound crystal structures suggests that these riboswitches achieve selectivity by enforcing heptacoordination (favored by high-spin Cd 2+ and Mn 2+ , but otherwise uncommon) in the softer site. Remarkably, the Cd 2+ - and Mn 2+ -selective bacterial transcription factor MntR also uses heptacoordination within a binuclear site to achieve selectivity. Published by Elsevier Ltd.

  18. Structure of the S. aureus PI-specific phospholipase C reveals modulation of active site access by a titratable π-cation latched loop†

    PubMed Central

    Goldstein, Rebecca; Cheng, Jiongjia; Stec, Boguslaw; Roberts, Mary F.

    2012-01-01

    Staphylococcus aureus secretes a phosphatidylinositol-specific phospholipase C (PIPLC) as a virulence factor that is unusual in exhibiting higher activity at acidic pH values than other enzymes in this class. We have determined the crystal structure of this enzyme at pH 4.6 and pH 7.5. Under slightly basic conditions, the S. aureus PI-PLC structure closely follows the conformation of other bacterial PI-PLCs. However, when crystallized under acidic conditions, a large section of mobile loop at the αβ-barrel rim in the vicinity of the active site shows ~10 Å shift. This loop displacement at acidic pH is the result of a titratable intramolecular π-cation interaction between His258 and Phe249. This was verified by a structure of the mutant protein H258Y crystallized at pH 4.6, which does not exhibit the large loop shift. The intramolecular π-cation interaction for S. aureus PI-PLC provides an explanation for the activity of the enzyme at acid pH and also suggests how phosphatidylcholine, as a competitor for Phe249, may kinetically activate this enzyme. PMID:22390775

  19. Polar Oxides without Inversion Symmetry through Vacancy and Chemical Order.

    PubMed

    Young, Joshua; Moon, Eun Ju; Mukherjee, Debangshu; Stone, Greg; Gopalan, Venkatraman; Alem, Nasim; May, Steven J; Rondinelli, James M

    2017-02-22

    One synthetic modality for materials discovery proceeds by forming mixtures of two or more compounds. In transition metal oxides (TMOs), chemical substitution often obeys Vegard's principle, and the resulting structure and properties of the derived phase follow from its components. A change in the assembly of the components into a digital nanostructure, however, can stabilize new polymorphs and properties not observed in the constituents. Here we formulate and demonstrate a crystal-chemistry design approach for realizing digital TMOs without inversion symmetry by combining two centrosymmetric compounds, utilizing periodic anion-vacancy order to generate multiple polyhedra that together with cation order produce a polar structure. We next apply this strategy to two brownmillerite-structured TMOs known to display centrosymmetric crystal structures in their bulk, Ca 2 Fe 2 O 5 and Sr 2 Fe 2 O 5 . We then realize epitaxial (SrFeO 2.5 ) 1 /(CaFeO 2.5 ) 1 thin film superlattices possessing both anion-vacancy order and Sr and Ca chemical order at the subnanometer scale, confirmed through synchrotron-based diffraction and aberration corrected electron microscopy. Through a detailed symmetry analysis and density functional theory calculations, we show that A-site cation ordering lifts inversion symmetry in the superlattice and produces a polar compound. Our results demonstrate how control of anion and cation order at the nanoscale can be utilized to produce acentric structures markedly different than their constituents and open a path toward novel structure-based property design.

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

    NASA Astrophysics Data System (ADS)

    Martin, M.; Schulz, O.

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

  1. Chemical Denudation and Cation Depletion in a Semi-Arid Catchment of the Long-Term Agroecological Research Observatory

    NASA Astrophysics Data System (ADS)

    Shaljian, M.; Keller, C. K.; Jones, K. B.; Brooks, E. S.; Huggins, D. R.

    2016-12-01

    The Long-Term Agroecosystem Research (LTAR) network of the USDA is a nationwide observatory and decadal-timescale field-experimental study of sustainable food production. The LTAR thus supports investigation of hydroecological and biogeochemical processes that could affect agricultural sustainability over the course of the 21st century. Mineral-derived nutrient cations are essential to fertility, and acidification of soils due to chemical fertilization may result in unsustainable chemical denudation of the soil exchange pool. Mineral weathering also contributes to base cation denudation. This study investigated base cation losses for one year in drainage from a semi-arid, rain-fed catchment at the Cook Agronomy Farm (CAF) LTAR site in southeastern Washington. We measured flows, analyzed drainage samples and estimated hydrologic effluxes of base cations from the catchment. The total dissolved base cation denudation rate at CAF-LTAR is about 40 kg ha-1 yr-1, which is comparable to other catchments on silicate terranes. The 2.1keq ha-1 yr-1 of denuded cationic charge is dominated by Ca2+ (61%) and Mg2+ (35%). Principal counter-ions are HCO3- (43%), NO3- (38%) and SO42- (16%), suggesting that both H2CO3 and HNO3 are important acids. Comparing 2008 soil pH and base saturation at CAF-LTAR to a nearby native prairie site, we preliminarily estimate a loss of 120 keq ha-1 of base cations from the upper 1.5m of the soil exchangeable cation pool. Dividing this depletion by the estimated denudation flux returns 60 years, which is approximately the interval of chemically intensive agriculture here. This may suggest that the source of exported base cations in drainage is primarily cation exchange rather than mineral weathering. The LTAR observatory will support ongoing monitoring and experimentation necessary to better understand base cation depletion and how it interacts with agroecological changes over the next several decades.

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

    PubMed

    Liang, Zhibin; Li, Qing X

    2018-04-04

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

  3. On the Structure-Property Relationships of Cation-Exchanged ZK-5 Zeolites for CO 2 Adsorption

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

    Pham, Trong D.; Hudson, Matthew R.; Brown, Craig M.

    2017-02-16

    The CO 2 adsorption properties of cation-exchanged Li-, Na-, K-, and Mg-ZK-5 zeolites were correlated to the molecular structures determined by Rietveld refinements of synchrotron powder X-ray diffraction patterns. Li-, K-, and Na-ZK-5 all exhibited high isosteric heats of adsorption (Qst) at low CO 2 coverage, with Na-ZK-5 having the highest Qst (ca. 49 kJ mol -1). Mg2+ was located at the center of the zeolite hexagonal prism with the cation inaccessible to CO 2, leading to a much lower Qst (ca. 30 kJ mol-1) and lower overall uptake capacity. Multiple CO 2 adsorption sites were identified at a givenmore » CO 2 loading amount for all four cation-exchanged ZK-5 adsorbents. Site A at the flat eight-membered ring windows and site B/B* in the γ-cages were the primary adsorption sites in Li - and Na-ZK-5 zeolites. Relatively strong dual-cation adsorption sites contributed significantly to an enhanced electrostatic interaction for CO 2 in all ZK-5 samples. This interaction gives rise to a migration of Li + and Mg 2+ cations from their original locations at the center of the hexagonal prisms toward the α-cages, in which they interact more strongly with the adsorbed CO 2.« less

  4. Strategies for generating peptide radical cations via ion/ion reactions.

    PubMed

    Gilbert, Joshua D; Fisher, Christine M; Bu, Jiexun; Prentice, Boone M; Redwine, James G; McLuckey, Scott A

    2015-02-01

    Several approaches for the generation of peptide radical cations using ion/ion reactions coupled with either collision induced dissociation (CID) or ultraviolet photo dissociation (UVPD) are described here. Ion/ion reactions are used to generate electrostatic or covalent complexes comprised of a peptide and a radical reagent. The radical site of the reagent can be generated multiple ways. Reagents containing a carbon-iodine (C-I) bond are subjected to UVPD with 266-nm photons, which selectively cleaves the C-I bond homolytically. Alternatively, reagents containing azo functionalities are collisionally activated to yield radical sites on either side of the azo group. Both of these methods generate an initial radical site on the reagent, which then abstracts a hydrogen from the peptide while the peptide and reagent are held together by either electrostatic interactions or a covalent linkage. These methods are demonstrated via ion/ion reactions between the model peptide RARARAA (doubly protonated) and various distonic anionic radical reagents. The radical site abstracts a hydrogen atom from the peptide, while the charge site abstracts a proton. The net result is the conversion of a doubly protonated peptide to a peptide radical cation. The peptide radical cations have been fragmented via CID and the resulting product ion mass spectra are compared to the control CID spectrum of the singly protonated, even-electron species. This work is then extended to bradykinin, a more broadly studied peptide, for comparison with other radical peptide generation methods. The work presented here provides novel methods for generating peptide radical cations in the gas phase through ion/ion reaction complexes that do not require modification of the peptide in solution or generation of non-covalent complexes in the electrospray process. Copyright © 2015 John Wiley & Sons, Ltd.

  5. Biopharmaceutical evaluation of epigallocatechin gallate-loaded cationic lipid nanoparticles (EGCG-LNs): In vivo, in vitro and ex vivo studies.

    PubMed

    Fangueiro, Joana F; Calpena, Ana C; Clares, Beatriz; Andreani, Tatiana; Egea, Maria A; Veiga, Francisco J; Garcia, Maria L; Silva, Amélia M; Souto, Eliana B

    2016-04-11

    Cationic lipid nanoparticles (LNs) have been tested for sustained release and site-specific targeting of epigallocatechin gallate (EGCG), a potential polyphenol with improved pharmacological profile for the treatment of ocular pathologies, such as age-related macular edema, diabetic retinopathy, and inflammatory disorders. Cationic EGCG-LNs were produced by double-emulsion technique; the in vitro release study was performed in a dialysis bag, followed by the drug assay using a previously validated RP-HPLC method. In vitro HET-CAM study was carried out using chicken embryos to determine the potential risk of irritation of the developed formulations. Ex vivo permeation profile was assessed using rabbit cornea and sclera isolated and mounted in Franz diffusion cells. The results show that the use of cationic LNs provides a prolonged EGCG release, following a Boltzmann sigmoidal profile. In addition, EGCG was successfully quantified in both tested ocular tissues, demonstrating the ability of these formulations to reach both anterior and posterior segment of the eye. The pharmacokinetic study of the corneal permeation showed a first order kinetics for both cationic formulations, while EGCG-cetyltrimethylammonium bromide (CTAB) LNs followed a Boltzmann sigmoidal profile and EGCG-dimethyldioctadecylammonium bromide (DDAB) LNs a first order profile. Our studies also proved the safety and non-irritant nature of the developed LNs. Thus, loading EGCG in cationic LNs is recognised as a promising strategy for the treatment of ocular diseases related to anti-oxidant and anti-inflammatory pathways. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Protonation switching to the least-basic heteroatom of carbamate through cationic hydrogen bonding promotes the formation of isocyanate cations.

    PubMed

    Kurouchi, Hiroaki; Sumita, Akinari; Otani, Yuko; Ohwada, Tomohiko

    2014-07-07

    We found that phenethylcarbamates that bear ortho-salicylate as an ether group (carbamoyl salicylates) dramatically accelerate OC bond dissociation in strong acid to facilitate generation of isocyanate cation (N-protonated isocyanates), which undergo subsequent intramolecular aromatic electrophilic cyclization to give dihydroisoquinolones. To generate isocyanate cations from carbamates in acidic media as electrophiles for aromatic substitution, protonation at the ether oxygen, the least basic heteroatom, is essential to promote CO bond cleavage. However, the carbonyl oxygen of carbamates, the most basic site, is protonated exclusively in strong acids. We found that the protonation site can be shifted to an alternative basic atom by linking methyl salicylate to the ether oxygen of carbamate. The methyl ester oxygen ortho to the phenolic (ether) oxygen of salicylate is as basic as the carbamate carbonyl oxygen, and we found that monoprotonation at the methyl ester oxygen in strong acid resulted in the formation of an intramolecular cationic hydrogen bond (>CO(+) H⋅⋅⋅O<) with the phenolic ether oxygen. This facilitates OC bond dissociation of phenethylcarbamates, thereby promoting isocyanate cation formation. In contrast, superacid-mediated diprotonation at the methyl ester oxygen of the salicylate and the carbonyl oxygen of the carbamate afforded a rather stable dication, which did not readily undergo CO bond dissociation. This is an unprecedented and unknown case in which the monocation has greater reactivity than the dication. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Cations Modulate Actin Bundle Mechanics, Assembly Dynamics, and Structure.

    PubMed

    Castaneda, Nicholas; Zheng, Tianyu; Rivera-Jacquez, Hector J; Lee, Hyun-Ju; Hyun, Jaekyung; Balaeff, Alexander; Huo, Qun; Kang, Hyeran

    2018-04-12

    Actin bundles are key factors in the mechanical support and dynamic reorganization of the cytoskeleton. High concentrations of multivalent counterions promote bundle formation through electrostatic attraction between actin filaments that are negatively charged polyelectrolytes. In this study, we evaluate how physiologically relevant divalent cations affect the mechanical, dynamic, and structural properties of actin bundles. Using a combination of total internal reflection fluorescence microscopy, transmission electron microscopy, and dynamic light scattering, we demonstrate that divalent cations modulate bundle stiffness, length distribution, and lateral growth. Molecular dynamics simulations of an all-atom model of the actin bundle reveal specific actin residues coordinate cation-binding sites that promote the bundle formation. Our work suggests that specific cation interactions may play a fundamental role in the assembly, structure, and mechanical properties of actin bundles.

  8. Adsorption of reovirus to clay minerals: effects of cation-exchange capacity, cation saturation, and surface area.

    PubMed Central

    Lipson, S M; Stotzky, G

    1983-01-01

    The adsorption of reovirus to clay minerals has been reported by several investigators, but the mechanisms defining this association have been studied only minimally. The purpose of this investigation was to elucidate the mechanisms involved with this interaction. More reovirus type 3 was adsorbed, in both distilled and synthetic estuarine water, by low concentrations of montmorillonite than by comparable concentrations of kaolinite containing a mixed complement of cations on the exchange complex. Adsorption to the clays was essentially immediate and was correlated with the cation-exchange capacity of the clays, indicating that adsorption was primarily to negatively charged sites on the clays. Adsorption was greater with low concentrations of clays in estuarine water than in distilled water, as the higher ionic strength of the estuarine water reduced the electrokinetic potential of both clay and virus particles. The addition of cations (as chloride salts) to distilled water enhanced adsorption, with divalent cations being more effective than monovalent cations and 10(-2) M resulting in more adsorption than 10(-3) M. Potassium ions suppressed reovirus adsorption to montmorillonite, probably by collapsing the clay lattices and preventing the expression of the interlayer-derived cation-exchange capacity. More virus was adsorbed by montmorillonite made homoionic to various mono-, di-, and trivalent cations (except by montmorillonite homoionic to potassium) than by comparable concentrations of kaolinite homoionic to the same cations. The sequence of the amount of adsorption to homoionic montmorillonite was Al greater than Ca greater than Mg greater than Na greater than K; the sequence of adsorption to kaolinite was Na greater than Al greater than Ca greater than Mg greater than K. The constant partition-type adsorption isotherms obtained when the clay concentration was maintained constant and the virus concentration was varied indicated that a fixed proportion of the

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

    PubMed

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

    2017-04-12

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

  10. Cation distribution and vacancies in nickel cobaltite.

    PubMed

    Loche, Danilo; Marras, Claudia; Carta, Daniela; Casula, Maria Francesca; Mountjoy, Gavin; Corrias, Anna

    2017-06-28

    Samples of nickel cobaltite, a mixed oxide occurring in the spinel structure which is currently extensively investigated because of its prospective application as ferromagnetic, electrocatalytic, and cost-effective energy storage material were prepared in the form of nanocrystals stabilized in a highly porous silica aerogel and as unsupported nanoparticles. Nickel cobaltite nanocrystals with average size 4 nm are successfully grown for the first time into the silica aerogel provided that a controlled oxidation of the metal precursor phases is carried out, consisting in a reduction under H 2 flow followed by mild oxidation in air. The investigation of the average oxidation state of the cations and of their distribution between the sites within the spinel structure, which is commonly described assuming the Ni cations are only located in the octahedral sites, has been carried out by X-ray absorption spectroscopy providing evidence for the first time that the unsupported nickel cobaltite sample has a Ni : Co molar ratio higher than the nominal ratio of 1 : 2 and a larger than expected average overall oxidation state of the cobalt and nickel cations. This is achieved retaining the spinel structure, which accommodates vacancies to counterbalance the variation in oxidation state.

  11. Natural zeolite reactivity towards ozone: the role of compensating cations.

    PubMed

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

    2012-08-15

    Among indoor pollutants, ozone is recognised to pose a threat to human health. Recently, low cost natural zeolites have been applied as alternative materials for ozone abatement. In this work, the effect of compensating cation content of natural zeolite on ozone removal is studied. A Chilean natural zeolite is used here as starting material. The amount of compensating cations in the zeolite framework was modified by ion exchange using an ammonium sulphate solution (0.1 mol L(-1)). Characterisation of natural and modified zeolites were performed by X-ray powder diffraction (XRD), nitrogen adsorption at 77K, elemental analysis, X-ray fluorescence (XRF), thermogravimetric analysis coupled with mass spectroscopy (TGA-MS), and temperature-programmed desorption of ammonia (NH(3)-TPD). Ozone adsorption and/or decomposition on natural and modified zeolites were studied by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Results show that the zeolite compensating cation content affects ozone interaction with zeolite active sites. Ammonium ion-exchange treatments followed by thermal out-gassing at 823 K, reduces ozone diffusion resistance inside the zeolite framework, increasing ozone abatement on zeolite surface active sites. Weak and strong Lewis acid sites of zeolite surface are identified here as the main active sites responsible of ozone removal. Copyright © 2012 Elsevier B.V. All rights reserved.

  12. Cation–cation interactions and cation exchange in a series of isostructural framework uranyl tungstates

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

    Balboni, Enrica; Burns, Peter C., E-mail: pburns@nd.edu; Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556

    2014-05-01

    The isotypical compounds (UO{sub 2}){sub 3}(WO{sub 6})(H{sub 2}O){sub 5} (1), Ag(UO{sub 2}){sub 3}(WO{sub 6})(OH)(H{sub 2}O){sub 3} (2), K(UO{sub 2}){sub 3}(WO{sub 6})OH(H{sub 2}O){sub 4} (3), Rb(UO{sub 2}){sub 3}(WO{sub 6})(OH)(H{sub 2}O){sub 3.5} (4), and Cs(UO{sub 2}){sub 3}(WO{sub 6})OH(H{sub 2}O){sub 3} (5) were synthesized, characterized, and their structures determined. Each crystallizes in space group Cc. (1): a=12.979 (3), b=10.238 (2), c=11.302 (2), β=102.044 (2); (2): a=13.148 (2), b=9.520 (1), c=11.083 (2), β=101.568 (2); (3): a=13.111 (8), b=9.930 (6), c=11.242 (7), β=101.024 (7); (4): a=12.940 (2), b=10.231 (2), c=11.259(2), β=102.205 (2); (5): a=12.983 (3), b=10.191 (3), c=11.263 (4), β=101.661 (4). Compounds 1–5 are amore » framework of uranyl and tungsten polyhedra containing cation–cation interactions. The framework has three symmetrically distinct U(VI) cations, one tungsten, sixteen to eighteen oxygen atoms, and in 2–5, one monovalent cation. Each atom occupies a general position. Each U(VI) cation is present as a typical (UO{sub 2}){sup 2+} uranyl ion in an overall pentagonal bipyramidal coordination environment. Each pentagonal bipyramid shares two equatorial edges with two other pentagonal bipyramids, forming a trimer. Trimers are connected into chains by edge-sharing with WO{sub 6} octahedra. Chains are linked through cation–cation interactions between two symmetrically independent uranyl ions. This yields a remarkably complex system of intersecting channels that extend along [0 0 1] and [−1 1 0]. The cation exchange properties of 2 and 3 were characterized at room temperature and at 140 °C. - Graphical abstract: Chains of uranium and tungsten polyhedra are connected into a three dimensional framework by cation–cation interactions occurring between two symmetrically independent uranyl pentagonal bipyramids. Monovalent cations present in channels within the structure can be exchanged by room temperature or mild

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

    PubMed Central

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

    2010-01-01

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

  14. Interactions between cations and peat organic matter monitored with NMR wideline, static and FFC NMR relaxometry

    NASA Astrophysics Data System (ADS)

    Schaumann, Gabriele E.; Conte, Pellegrino; Jäger, Alexander; Alonzo, Giuseppe; Bertmer, Marko

    2010-05-01

    The molecular size of humic substances is still under debate and is believed to range up to several hundred thousands Dalton, although a number of recent studies suggest much lower molecular weights. Nowadays an increasing number of authors suggest a model of molecular aggregates. One explanation why results on the molecular mass of humic materials are contradictory, may be that individual OM molecules are linked via intermolecular interactions, by bridges of water molecules or by cations bridging cation exchange sites (Schaumann, 2006a, b). Properties of such cross-linked systems can be similar to macromolecular systems revealing covalent cross-links. In this context, multivalent cations play an important ecological role, serving as reversible cross-linking agent. Formation and disruption of such cation bridges may close or open sorption sites in soil organic matter. Although cross-linking by multivalent cations has been proposed in many studies, the cross-linking effect has not yet been demonstrated on the molecular scale. The objective of this study was to investigate the interactions between cations and peat organic matter using NMR wideline techniques as well as static and fast field cycling (FFC) NMR relaxometry. Peat treated with solutions containing either Na+, Ca2+ or Al3+ was investigated in air-dried state for longitudinal relaxation times (T1) and NMR wideline characteristics. T1 distributions were separated into two Gaussian functions which were interpreted to represent two proton populations belonging to two environments of differing mobility. The relaxation rates (R1 = T1-1) in the cation treated samples spread over a range of 87-123 s-1 (R1a: fast component) and 32-42 s-1 (R1b: slow component). The rates in all treatments are significantly different from each other. and decrease in the order conditioned sample > desalinated sample > Na-treated sample. The treatment with multivalent cations affects R1a and R1b in different ways and needs more

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

    PubMed

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

    2015-02-03

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

  16. Cation-exchanged zeolites for the selective oxidation of methane to methanol

    DOE PAGES

    Kulkarni, Ambarish R.; Zhao, Zhi-Jian; Siahrostami, Samira; ...

    2017-10-19

    Motivated by the increasing availability of cheap natural gas resources, considerable experimental and computational research efforts have focused on identifying selective catalysts for the direct conversion of methane to methanol. One promising class of catalysts are cation-exchanged zeolites, which have steadily increased in popularity over the past decade. Here, in this article, we first present a broad overview of this field from a conceptual perspective, and highlight the role of theory in developing a molecular-level understanding of the reaction. Next, by performing and analyzing a large database of density functional theory (DFT) calculations for a wide range of transition metalmore » cations, zeolite topologies and active site motifs, we present a unifying picture of the methane activation process in terms of active site stability, C–H bond activation and methanol extraction. Based on the trade-offs of active site stability and reactivity, we propose a framework for identifying new, promising active site motifs in these systems. Further, we show that the high methanol selectivity arises due to the strong binding nature of the C–H activation products. Lastly, using the atomistic and mechanistic insight obtained from these analyses, we summarize the key challenges and future strategies for improving the performance of cation-exchanged zeolites for this industrially relevant conversion.« less

  17. Cation-exchanged zeolites for the selective oxidation of methane to methanol

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

    Kulkarni, Ambarish R.; Zhao, Zhi-Jian; Siahrostami, Samira

    Motivated by the increasing availability of cheap natural gas resources, considerable experimental and computational research efforts have focused on identifying selective catalysts for the direct conversion of methane to methanol. One promising class of catalysts are cation-exchanged zeolites, which have steadily increased in popularity over the past decade. Here, in this article, we first present a broad overview of this field from a conceptual perspective, and highlight the role of theory in developing a molecular-level understanding of the reaction. Next, by performing and analyzing a large database of density functional theory (DFT) calculations for a wide range of transition metalmore » cations, zeolite topologies and active site motifs, we present a unifying picture of the methane activation process in terms of active site stability, C–H bond activation and methanol extraction. Based on the trade-offs of active site stability and reactivity, we propose a framework for identifying new, promising active site motifs in these systems. Further, we show that the high methanol selectivity arises due to the strong binding nature of the C–H activation products. Lastly, using the atomistic and mechanistic insight obtained from these analyses, we summarize the key challenges and future strategies for improving the performance of cation-exchanged zeolites for this industrially relevant conversion.« less

  18. Restructuring of a Peat in Interaction with Multivalent Cations: Effect of Cation Type and Aging Time

    PubMed Central

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

    2013-01-01

    It is assumed to be common knowledge that multivalent cations cross-link soil organic matter (SOM) molecules via cation bridges (CaB). The concept has not been explicitly demonstrated in solid SOM by targeted experiments, yet. Therefore, the requirements for and characteristics of CaB remain unidentified. In this study, a combined experimental and molecular modeling approach was adopted to investigate the interaction of cations on a peat OM from physicochemical perspective. Before treatment with salt solutions of Al3+, Ca2+ or Na+, respectively, the original exchangeable cations were removed using cation exchange resin. Cation treatment was conducted at two different values of pH prior to adjusting pH to 4.1. Cation sorption is slower (>>2 h) than deprotonation of functional groups (<2 h) and was described by a Langmuir model. The maximum uptake increased with pH of cation addition and decreased with increasing cation valency. Sorption coefficients were similar for all cations and at both pH. This contradicts the general expectations for electrostatic interactions, suggesting that not only the interaction chemistry but also spatial distribution of functional groups in OM determines binding of cations in this peat. The reaction of contact angle, matrix rigidity due to water molecule bridges (WaMB) and molecular mobility of water (NMR analysis) suggested that cross-linking via CaB has low relevance in this peat. This unexpected finding is probably due to the low cation exchange capacity, resulting in low abundance of charged functionalities. Molecular modeling demonstrates that large average distances between functionalities (∼3 nm in this peat) cannot be bridged by CaB-WaMB associations. However, aging strongly increased matrix rigidity, suggesting successive increase of WaMB size to connect functionalities and thus increasing degree of cross-linking by CaB-WaMB associations. Results thus demonstrated that the physicochemical structure of OM is decisive for Ca

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

    PubMed

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

    2013-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

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

  1. Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes

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

    Wang, Dawei; Kou, Ronghui; Ren, Yang

    Nickel-rich layered transition metal oxides, LiNi1-x(MnCo)(x)O-2 (1-x >= 0.5), are appealing candidates for cathodes in next-generation lithium-ion batteries (LIBs) for electric vehicles and other large-scale applications, due to their high capacity and low cost. However, synthetic control of the structural ordering in such a complex quaternary system has been a great challenge, especially in the presence of high Ni content. Herein, synthesis reactions for preparing layered LiNi0.7Mn0.15Co0.15O2 (NMC71515) by solid-state methods are investigated through a combination of time-resolved in situ high-energy X-ray diffraction and absorption spectroscopy measurements. The real-time observation reveals a strong temperature dependence of the kinetics of cationicmore » ordering in NMC71515 as a result of thermal-driven oxidation of transition metals and lithium/oxygen loss that concomitantly occur during heat treatment. Through synthetic control of the kinetic reaction pathway, a layered NMC71515 with low cationic disordering and a high reversible capacity is prepared in air. The findings may help to pave the way for designing high-Ni layered oxide cathodes for LIBs.« less

  2. Sorption of the organic cation metoprolol on silica gel from its aqueous solution considering the competition of inorganic cations.

    PubMed

    Kutzner, Susann; Schaffer, Mario; Börnick, Hilmar; Licha, Tobias; Worch, Eckhard

    2014-05-01

    Systematic batch experiments with the organic monovalent cation metoprolol as sorbate and the synthetic material silica gel as sorbent were conducted with the aim of characterizing the sorption of organic cations onto charged surfaces. Sorption isotherms for metoprolol (>99% protonated in the tested pH of around 6) in competition with mono- and divalent inorganic cations (Na(+), NH4(+), Ca(2+), and Mg(2+)) were determined in order to assess their influence on cation exchange processes and to identify the role of further sorptive interactions. The obtained sorption isotherms could be described well by an exponential function (Freundlich isotherm model) with consistent exponents (about 0.8). In general, a decreasing sorption of metoprolol with increasing concentrations in inorganic cations was observed. Competing ions of the same valence showed similar effects. A significant sorption affinity of metoprolol with ion type dependent Freundlich coefficients KF,0.77 between 234.42 and 426.58 (L/kg)(0.77) could still be observed even at very high concentrations of competing inorganic cations. Additional column experiments confirm this behavior, which suggests the existence of further relevant interactions beside cation exchange. In subsequent batch experiments, the influence of mixtures with more than one competing ion and the effect of a reduced negative surface charge at a pH below the point of zero charge (pHPZC ≈ 2.5) were also investigated. Finally, the study demonstrates that cation exchange is the most relevant but not the sole mechanism for the sorption of metoprolol on silica gel. Copyright © 2014 Elsevier Ltd. All rights reserved.

  3. Shifting the equilibrium mixture of gramicidin double helices toward a single conformation with multivalent cationic salts.

    PubMed Central

    Doyle, D A; Wallace, B A

    1998-01-01

    The conformation of the polypeptide antibiotic gramicidin is greatly influenced by its environment. In methanol, it exists as an equilibrium mixture of four interwound double-helical conformers that differ in their handedness, chain orientation, and alignment. Upon the addition of multivalent cationic salts, there is a shift in the equilibrium to a single conformer, which was monitored in this study by circular dichroism spectroscopy. With increasing concentrations of multivalent cations, both the magnitude of the entire spectrum and the ratio of the 229-nm to the 210-nm peak were increased. The spectral change is not related to the charge on the cation, but appears to be related to the cationic radius, with the maximum change in ellipticity occurring for cations with a radius of approximately 1 A. The effect requires the presence of an anion whose radius is greater than that of a fluoride ion, but is otherwise not a function of anion type. It is postulated that multivalent cations interact with a binding site in one of the conformers, known as species 1 (a left-handed, parallel, no stagger double helix), stabilizing a modified form of this type of structure. PMID:9675165

  4. Cooperativity and complexity in the binding of anions and cations to a tetratopic ion-pair host.

    PubMed

    Howe, Ethan N W; Bhadbhade, Mohan; Thordarson, Pall

    2014-05-21

    Cooperative interactions play a very important role in both natural and synthetic supramolecular systems. We report here on the cooperative binding properties of a tetratopic ion-pair host 1. This host combines two isophthalamide anion recognition sites with two unusual "half-crown/two carbonyl" cation recognition sites as revealed by the combination of single-crystal X-ray analysis of the free host and the 1:2 host:calcium cation complex, together with two-dimensional NMR and computational studies. By systematically comparing all of the binding data to several possible binding models and focusing on four different variants of the 1:2 binding model, it was in most cases possible to quantify these complex cooperative interactions. The data showed strong negative cooperativity (α = 0.01-0.05) of 1 toward chloride and acetate anions, while for cations the results were more variable. Interestingly, in the competitive (CDCl3/CD3OD (9:1, v/v)) solvent, the addition of calcium cations to the tetratopic ion-pair host 1 allosterically switched "on" chloride binding that is otherwise not present in this solvent system. The insight into the complexity of cooperative interactions revealed in this study of the tetratopic ion-pair host 1 can be used to design better cooperative supramolecular systems for information transfer and catalysis.

  5. Differential Cationization of Fatty Acids with Monovalent Cations Studied by ESI-MS/MS and Computational Approach.

    PubMed

    Sudarshana Reddy, B; Pavankumar, P; Sridhar, L; Saha, Soumen; Narahari Sastry, G; Prabhakar, S

    2018-04-24

    The intercellular and intracellular transport of charged species (Na + /K + ) entail interaction of the ions with neutral organic molecules and formation of adduct ions. The rate of transport of the ions across the cell membrane(s) may depend on the stability of the adduct ions, which in turn rely on structural aspects of the organic molecules that interact with the ions. Positive ion ESI mass spectra were recorded for the solutions containing fatty acids (FAs) and monovalent cations (X=Li + , Na + , K + , Rb + and Cs + ). Product ion spectra of the [FA+X] + ions were recorded at different collision energies. Theoretical studies were exploited under both gas phase and solvent phase to investigate the structural effects of the fatty acids during cationization. Stability of [FA+X] + adduct ions were further estimated by means of AIM topological analyses and interaction energy (IE) values. Positive ion ESI-MS analyses of the solution of FAs and X + ions showed preferential binding of the K + ions to FAs. The K + ion binding increased with the increase in number of double bonds of FAs, while decreased with increase in the number of carbons of FAs. Dissociation curves of [FA+X] + ions indicated the relative stability order of the [FA+X] + ions and it was in line with the observed trends in ESI-MS. The solvent phase computational studies divulged the mode of binding and the binding efficiencies of different FAs with monovalent cations. Among the studied monovalent cations, the cationization of FAs follow the order K + >Na + >Li + >Rb + >Cs + . The docosahexaenoic acid showed high efficiency in binding with K + ion. The K + ion binding efficiency of FAs depends on the number of double bonds in unsaturated FAs and the carbon chain length in saturated FAs. The cationization trends of FAs obtained from the ESI-MS, ESI-MS/MS analyses were in good agreement with solvent phase computational studies. This article is protected by copyright. All rights reserved.

  6. Sorption of organic cations onto silica surfaces over a wide concentration range of competing electrolytes.

    PubMed

    Kutzner, Susann; Schaffer, Mario; Licha, Tobias; Worch, Eckhard; Börnick, Hilmar

    2016-12-15

    The fundamental understanding of organic cation-solid phase interactions is essential for improved predictions of the transport and ultimate environmental fates of widely used substances (e.g., pharmaceutical compounds) in the aquatic environment. We report sorption experiments of two cationic model compounds using two silica gels and a natural aquifer sediment. The sorbents were extensively characterized and the results of surface titrations under various background electrolyte concentrations were discussed. The salt dependency of sorption was systematically studied in batch experiments over a wide concentration range (five orders of magnitude) of inorganic ions in order to examine the influence of increasing competition on the sorption of organic cations. The organic cation uptake followed the Freundlich isotherm model and the sorption capacity decreases with an increase in the electrolyte concentration due to the underlying cation exchange processes. However, the sorption recovers considerably at high ionic strength (I>1M). To our knowledge, this effect has not been observed before and appears to be independent from the sorbent characteristics and sorbate structure. Furthermore, the recovery of sorption was attributed to specific, non-ionic interactions and a connection between the sorption coefficient and activity coefficient of the medium is presumed. Eventually, the reasons for the differing sorption affinities of both sorbates are discussed. Copyright © 2016 Elsevier Inc. All rights reserved.

  7. Capability of cation exchange technology to remove proven N-nitrosodimethylamine precursors.

    PubMed

    Li, Shixiang; Zhang, Xulan; Bei, Er; Yue, Huihui; Lin, Pengfei; Wang, Jun; Zhang, Xiaojian; Chen, Chao

    2017-08-01

    N-nitrosodimethylamine (NDMA) precursors consist of a positively charged dimethylamine group and a non-polar moiety, which inspired us to develop a targeted cation exchange technology to remove NDMA precursors. In this study, we tested the removal of two representative NDMA precursors, dimethylamine (DMA) and ranitidine (RNTD), by strong acidic cation exchange resin. The results showed that pH greatly affected the exchange efficiency, with high removal (DMA>78% and RNTD>94%) observed at pHa -1 when the molar ratio of exchange capacity to precursor was 4. The exchange order was obtained as follows: Ca 2+ >Mg 2+ >RNTD + >K + >DMA + >NH 4 + >Na + . The partition coefficient of DMA + to Na + was 1.41±0.26, while that of RNTD + to Na + was 12.1±1.9. The pseudo second-order equation fitted the cation exchange kinetics well. Bivalent inorganic cations such as Ca 2+ were found to have a notable effect on NA precursor removal in softening column test. Besides DMA and RNTD, cation exchange process also worked well for removing other 7 model NDMA precursors. Overall, NDMA precursor removal can be an added benefit of making use of cation exchange water softening processes. Copyright © 2017. Published by Elsevier B.V.

  8. Formation of reactive oxygen by N2O decomposition over binuclear cationic sites of Fe-ferrierite zeolite: Periodic DFT + U study

    NASA Astrophysics Data System (ADS)

    Avdeev, Vasilii I.; Bedilo, Alexander F.

    2018-03-01

    The electronic nature of sites over Fe-ferrierite zeolite stabilizing active α-oxygen is analyzed by the periodic DFT + U approach. It is shown that two antiferromagnetically coupled Fe2+ cations with bridging OH-bonds form a stable bi-nuclear site of the [Fe2+<2OH>Fe2+] doped FER complex. Frontier orbitals of this complex populated by two electrons with minority spins are localized in the bandgap. As a result, [Fe2+<2OH>Fe2+] unit acquires the properties of a binuclear Lewis acid dipolarophile for 1,3-dipole N2O. First reaction step of N2O decomposition follows the Huisgen‧s concept of the 1,3-dipolar cycloaddition concept followed by the formation of reactive oxygen species Fesbnd O.

  9. The regulation of integrin function by divalent cations

    PubMed Central

    Zhang, Kun; Chen, JianFeng

    2012-01-01

    Integrins are a family of α/β heterodimeric adhesion metalloprotein receptors and their functions are highly dependent on and regulated by different divalent cations. Recently advanced studies have revolutionized our perception of integrin metal ion-binding sites and their specific functions. Ligand binding to integrins is bridged by a divalent cation bound at the MIDAS motif on top of either α I domain in I domain-containing integrins or β I domain in α I domain-less integrins. The MIDAS motif in β I domain is flanked by ADMIDAS and SyMBS, the other two crucial metal ion binding sites playing pivotal roles in the regulation of integrin affinity and bidirectional signaling across the plasma membrane. The β-propeller domain of α subunit contains three or four β-hairpin loop-like Ca2+-binding motifs that have essential roles in integrin biogenesis. The function of another Ca2+-binding motif located at the genu of α subunit remains elusive. Here, we provide an overview of the integrin metal ion-binding sites and discuss their roles in the regulation of integrin functions. PMID:22647937

  10. Local crystal/chemical structures at iron sites in amorphous, magnetic, and nanocrystalline materials

    NASA Astrophysics Data System (ADS)

    Clark, Ted Michael

    Order-disorder phenomena have been examined by means of Mossbauer spectroscopy in a variety of materials, including (a) tektites and other silicate glasses, (b) magnetic materials such as natural and synthetic magnetoplumbite, M-type hexagonal ferrites and magnetite, and (c) nanocrystalline zinc ferrite. A methodology has been established for the analysis of the local crystal/chemical structures of iron in tektites and its application has reconfirmed a low ferric/ferrous ratio of approximately 0.10 for tektites. Additionally, a greater degree of submirocscopic heterogeneity has been established for Muong Nong tektites in comparison with splash form tektites. The dynamics of the 2b site in hexagonal ferrites has been studied above and below the Curie temperature for magnetoplumbite and its synthetic analogs, and also for polycrystalline and oriented single-crystals of MeFesb{12}Osb{19} (Me=Ba, Sr, Pb). Cation ordering on this site is shown to be dependent on the thermal history of the material, while the dynamic disorder of the 2b site for the end-member hexagonal ferrites is shown to be influenced by the divalent heavy metal species, Me. The influence of chemical composition on the morphology of magnetite has been shown to depend on the site preference of impurity cations: Substitutional impurities with tetrahedral site preferences are postulated to result in the seldom-observed cubic habit. Based on the cation distributions of bulk and nanocrystalline material it is held that the enhanced magnetic moments and susceptibilities of nanocrystalline zinc ferrite are shown to be consistent with surface phenomena, independent of synthesis methodology, and contrary to claims of special effects resulting from a particular synthesis methodology.

  11. Impact of managed moorland burning on peat nutrient and base cation status

    NASA Astrophysics Data System (ADS)

    Palmer, Sheila; Gilpin, Martin; Wearing, Catherine; Johnston, Kerrylyn; Holden, Joseph; Brown, Lee

    2013-04-01

    Controlled 'patch' burning of moorland vegetation has been used for decades in the UK to stimulate growth of heather (Calluna vulgaris) for game bird habitat and livestock grazing. Typically small patches (300-900 m2) are burned in rotations of 8-25 years. However, our understanding of the short-to-medium term environmental impacts of the practice on these sensitive upland areas has so far been limited by a lack of scientific data. In particular the effect of burning on concentrations of base cations and acid-base status of these highly organic soils has implications both for ecosystem nutrient status and for buffering of acidic waters. As part of the EMBER project peat chemistry data were collected in ten upland blanket peat catchments in the UK. Five catchments were subject to a history of prescribed rotational patch burning. The other five catchments acted as controls which were not subject to burning, nor confounded by other detrimental activities such as drainage or forestry. Soil solution chemistry was also monitored at two intensively studied sites (one regularly burned and one control). Fifty-centimetre soil cores, sectioned into 5-cm intervals, were collected from triplicate patches of four burn ages at each burned site, and from twelve locations at similar hillslope positions at each control site. At the two intensively monitored sites, soil solution chemistry was monitored at four depths in each patch. Across all sites, burned plots had significantly smaller cation exchange capacities, lower concentrations of exchangeable base cations and increased concentrations of exchangeable H+ and Al3+ in near-surface soil. C/N ratios were also lower in burned compared to unburned surface soils. There was no consistent trend between burn age and peat chemistry across all burned sites, possibly reflecting local controls on post-burn recovery rates or external influences on burn management decisions. At the intensively monitored site, plots burned less than two years

  12. Enhanced charge ordering transition in doped CaFeO3 through steric templating

    NASA Astrophysics Data System (ADS)

    Jiang, Lai; Saldana-Greco, Diomedes; Schick, Joseph T.; Rappe, Andrew M.

    2014-06-01

    We report a density functional theory investigation of B-site doped CaFeO3, a prototypical charge ordered perovskite. At 290 K, CaFeO3 undergoes a metal-insulator transition and a charge disproportionation reaction 2Fe4+→Fe5++Fe3+. We observe that when Zr dopants occupy a (001) layer, the band gap of the resulting solid solution increases to 0.93 eV due to a two-dimensional Jahn-Teller-type distortion, where FeO6 cages on the xy plane elongate along x and y alternatively between neighboring Fe sites. Furthermore, we show that the rock-salt ordering of the Fe5+ and Fe3+ cations can be enhanced when the B-site dopants are arranged in a (111) plane due to a collective steric effect that facilitates the size discrepancy between the Fe5+O6 and Fe3+O6 octahedra and therefore gives rise to a larger band gap. The enhanced charge disproportionation in these solid solutions is verified by rigorously calculating the oxidation states of the Fe cations with different octahedral cage sizes. We therefore predict that the corresponding transition temperature will increase due to the enhanced charge ordering and larger band gap. The compositional, structural, and electrical relationships exploited in this paper can be extended to a variety of perovskites and nonperovskite oxides, providing guidance in the structural manipulation of electrical properties of functional materials.

  13. The infrared signature of water associated with trivalent cations in olivine

    NASA Astrophysics Data System (ADS)

    Berry, Andrew J.; O'Neill, Hugh St. C.; Hermann, Jörg; Scott, Dean R.

    2007-09-01

    Forsterite crystals were synthesised under water saturated conditions at 1400 °C and 1.5 GPa doped with trace amounts of either B, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ga, Y, Zr, In, Sm, Gd, Dy, Tm, or Lu. The common and intense hydroxyl stretching bands in the infrared spectra of spinel peridotite olivine, at 3572 and 3525 cm -1, were only reproduced in the presence of Ti. Those samples where the trace element substitutes as the trivalent cation on the Mg 2+ site were identified from a systematic variation in concentration with the trivalent ionic radius. The hydroxyl region of all samples is essentially identical except for between 3300 and 3400 cm -1. This region is characterised by one or more bands, with the energy of the most intense feature being correlated with the ionic radius of the trivalent cation. The integrated intensity of these hydroxyl bands also correlates with the concentration of the trivalent cation. These correlations provide unambiguous evidence that bands, or peaks, in this region correspond to water at defect sites associated with trivalent cations. "Trivalent peaks" are sometimes observed in samples of mantle olivine and most likely indicate water associated with Fe 3+. The water at this site is not incorporated under normal mantle conditions and should not be included in estimates of the water capacity of mantle olivine. These results emphasise the importance of identifying the infrared signature of different water substitution mechanisms.

  14. Cationic antimicrobial peptides in penaeid shrimp.

    PubMed

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

    2011-08-01

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

  15. Hydration of cations: a key to understanding of specific cation effects on aggregation behaviors of PEO-PPO-PEO triblock copolymers.

    PubMed

    Lutter, Jacob C; Wu, Tsung-yu; Zhang, Yanjie

    2013-09-05

    This work reports results from the interactions of a series of monovalent and divalent cations with a triblock copolymer, poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO). Phase transition temperatures of the polymer in the presence of chloride salts with six monovalent and eight divalent cations were measured using an automated melting point apparatus. The polymer undergoes a two-step phase transition, consisting of micellization of the polymer followed by aggregation of the micelles, in the presence of all the salts studied herein. The results suggest that hydration of cations plays a key role in determining the interactions between the cations and the polymer. The modulation of the phase transition temperature of the polymer by cations can be explained as a balance between three interactions: direct binding of cations to the oxygen in the polymer chains, cations sharing one water molecule with the polymer in their hydration layer, and cations interacting with the polymer via two water molecules. Monovalent cations Na(+), K(+), Rb(+), and Cs(+) do not bind to the polymer, while Li(+) and NH4(+) and all the divalent cations investigated including Mg(2+), Ca(2+), Sr(2+), Ba(2+), Co(2+), Ni(2+), Cu(2+), and Cd(2+) bind to the polymer. The effects of the cations correlate well with their hydration thermodynamic properties. Mechanisms for cation-polymer interactions are discussed.

  16. Cation distribution and optical properties of Cr-doped MgGa2O4 nanocrystals

    NASA Astrophysics Data System (ADS)

    Duan, Xiulan; Liu, Jian; Wang, Xinqiang; Jiang, Huaidong

    2014-11-01

    The distribution of cations in the spinel-type MgCr2yGa2-2yO4 (y = 0-0.6) nanocrystals and their optical properties as a function of annealing temperature and chromium content were investigated by using X-ray photoelectron spectroscopy (XPS) in combination with absorption spectroscopy. The cations in MgCr2yGa2-2yO4 nanocrystals are disorderly distributed with mixing of divalent and trivalent cations occupying the tetrahedral and octahedral sites. With the increase of annealing temperature, the inversion parameter (the fraction of Mg2+ ions in octahedral sites) decreases, which has the same varying tendency with the proportion of tetrahedral Ga3+ or Cr3+ ions. The inversion parameter increases with increasing Cr3+ concentration. The absorption spectra indicate that Cr3+ ions are located in the octahedral sites as well as in the tetrahedral sites. The fraction of tetrahedral Cr3+ decreases with Cr-enrichment. The optical absorption properties of Cr-doped MgGa2O4 nanocrystals may be tuned by varying the preparation temperature or Cr concentration.

  17. A hydrophobic filter confers the cation selectivity of Zygosaccharomyces rouxii plasma-membrane Na+/H+ antiporter.

    PubMed

    Kinclova-Zimmermannova, Olga; Falson, Pierre; Cmunt, Denis; Sychrova, Hana

    2015-04-24

    Na(+)/H(+) antiporters may recognize all alkali-metal cations as substrates but may transport them selectively. Plasma-membrane Zygosaccharomyces rouxii Sod2-22 antiporter exports Na(+) and Li(+), but not K(+). The molecular basis of this selectivity is unknown. We combined protein structure modeling, site-directed mutagenesis, phenotype analysis and cation efflux measurements to localize and characterize the cation selectivity region. A three-dimensional model of the ZrSod2-22 transmembrane domain was generated based on the X-ray structure of the Escherichia coli NhaA antiporter and primary sequence alignments with homologous yeast antiporters. The model suggested a close proximity of Thr141, Ala179 and Val375 from transmembrane segments 4, 5 and 11, respectively, forming a hydrophobic hole in the putative cation pathway's core. A series of mutagenesis experiments verified the model and showed that structural modifications of the hole resulted in altered cation selectivity and transport activity. The triple ZrSod2-22 mutant T141S-A179T-V375I gained K(+) transport capacity. The point mutation A179T restricted the antiporter substrate specificity to Li(+) and reduced its transport activity, while serine at this position preserved the native cation selectivity. The negative effect of the A179T mutation can be eliminated by introducing a second mutation, T141S or T141A, in the preceding transmembrane domain. Our experimental results confirm that the three residues found through modeling play a central role in the determination of cation selectivity and transport activity in Z. rouxii Na(+)/H(+) antiporter and that the cation selectivity can be modulated by repositioning a single local methyl group. Copyright © 2015 Elsevier Ltd. All rights reserved.

  18. Cation Distribution and Magnetism in Quenched ZnFe2O4

    NASA Astrophysics Data System (ADS)

    Yuan, Qiao; Pan, Linlin; Liu, Run; Wang, Jingming; Liao, Zuzhen; Qin, Lili; Bi, Jian; Gao, Daojiang; Wu, Jiangtao

    2018-03-01

    Spinel ferrites constitute one of the most important families of magnets; their properties are believed to be highly dependent on cation occupancy. Zinc ferrite materials synthesized by various methods are usually reported to exhibit enhanced magnetism, but the mechanism underlying such enhancement remains poorly understood, with at least three effects being considered, namely cation distribution, oxygen vacancies, and surface spin disorder. We report herein the individual influence of cation distribution on the magnetic properties of zinc ferrite microparticles, synthesized by solid-state reaction with a fast (200 K/s) quench process. Based on structure analyses including x-ray powder diffraction, scanning electron microscopy, x-ray photoelectron spectroscopy, Mössbauer spectroscopy, and magnetic measurements, it is concluded that the as-prepared samples exhibited different cation distribution with inversion degree increasing from approximately 0.18 to 0.28 with increasing calcination temperature from 800°C to 1200°C. The magnetism measured at 2 K was found to be enhanced with increase of the inversion degree, while that measured at 300 K was found to be independent of inversion degree. The mechanism of the enhanced magnetization is that the indirect interaction between A and B site at low temperature is stronger than that between two nearest B sites.

  19. Cation Distribution and Magnetism in Quenched ZnFe2O4

    NASA Astrophysics Data System (ADS)

    Yuan, Qiao; Pan, Linlin; Liu, Run; Wang, Jingming; Liao, Zuzhen; Qin, Lili; Bi, Jian; Gao, Daojiang; Wu, Jiangtao

    2018-07-01

    Spinel ferrites constitute one of the most important families of magnets; their properties are believed to be highly dependent on cation occupancy. Zinc ferrite materials synthesized by various methods are usually reported to exhibit enhanced magnetism, but the mechanism underlying such enhancement remains poorly understood, with at least three effects being considered, namely cation distribution, oxygen vacancies, and surface spin disorder. We report herein the individual influence of cation distribution on the magnetic properties of zinc ferrite microparticles, synthesized by solid-state reaction with a fast (200 K/s) quench process. Based on structure analyses including x-ray powder diffraction, scanning electron microscopy, x-ray photoelectron spectroscopy, Mössbauer spectroscopy, and magnetic measurements, it is concluded that the as-prepared samples exhibited different cation distribution with inversion degree increasing from approximately 0.18 to 0.28 with increasing calcination temperature from 800°C to 1200°C. The magnetism measured at 2 K was found to be enhanced with increase of the inversion degree, while that measured at 300 K was found to be independent of inversion degree. The mechanism of the enhanced magnetization is that the indirect interaction between A and B site at low temperature is stronger than that between two nearest B sites.

  20. Small Water Cluster Cations

    NASA Astrophysics Data System (ADS)

    Novakovskaya, Yu. V.; Stepanov, N. F.

    Structures of water cluster cations (H_{2}O)^{+}_{n} with n ≤ 5 are optimized at the unrestricted Hartree-Fock level with the 4 - 31 + +G** basis set. Energetic characteristics of the cations are then estimated taking into account the second order perturbation corrections (MP2). After the electron detachment from a neutral cluster, the structure of the latter substantially changes, so that OH and H3O+ fragments can be distinguished in it. In some cations H3O+ is so strongly bonded to water molecules that it is reasonable to speak of the [H2n-1On-1]+ fragments. According to the position of OH, the structures form two groups. In one group, OH acts exclusively as the proton acceptor in H-bonds with water molecules, thus being terminal in the chain-like structures; in the other group it is directly bonded to H3O and, as a proton donor, forms an H-bond with water molecule. Cluster cations do not tend to dissociate into the fragments. However, an external influence of ≤ 0.4 eV is sufficient for the cations of the first group to dissociate into a free OH radical and a protonated cluster H+(H2O)n-1. Extrapolation of the calculated adiabatic ionization potentials of the water clusters to n → ∞ provides a value of 8.6 eV, which can be considered as an estimation of the electron work function of water. This value is close to the experimental photoelectric thresholds of amorphous ice (8.7 ± 0.1 eV) and water (9.39 ± 0.3 eV). Solvation of the electron lowers the value, and an energy of 7 eV can be sufficient for initiating conductivity. This prediction is in accord with the experiment: irradiating ice with ultraviolet light of the photon energy 6.5-6.8 eV initiates photoconductivity, and hydrogen peroxide and H3O+ ions are observed.

  1. Watson-Crick Base Pair Radical Cation as a Model for Oxidative Damage in DNA.

    PubMed

    Feketeová, Linda; Chan, Bun; Khairallah, George N; Steinmetz, Vincent; Maitre, Philippe; Radom, Leo; O'Hair, Richard A J

    2017-07-06

    The deleterious cellular effects of ionizing radiation are well-known, but the mechanisms causing DNA damage are poorly understood. The accepted molecular events involve initial oxidation and deprotonation at guanine sites, triggering hydrogen atom abstraction reactions from the sugar moieties, causing DNA strand breaks. Probing the chemistry of the initially formed radical cation has been challenging. Here, we generate, spectroscopically characterize, and examine the reactivity of the Watson-Crick nucleobase pair radical cation in the gas phase. We observe rich chemistry, including proton transfer between the bases and propagation of the radical site in deoxyguanosine from the base to the sugar, thus rupturing the sugar. This first example of a gas-phase model system providing molecular-level details on the chemistry of an ionized DNA base pair paves the way toward a more complete understanding of molecular processes induced by radiation. It also highlights the role of radical propagation in chemistry, biology, and nanotechnology.

  2. Cation distribution in NiZn-ferrite films via extended x-ray absorption fine structure

    NASA Astrophysics Data System (ADS)

    Harris, V. G.; Koon, N. C.; Williams, C. M.; Zhang, Q.; Abe, M.; Kirkland, J. P.

    1996-04-01

    We have applied extended x-ray absorption fine structure (EXAFS) spectroscopy to study the cation distribution in a series of spin-sprayed NiZn-ferrite films. A least-squares fitting of experimental EXAFS data with theoretical, multiple-scattering, EXAFS data allowed the quantitative determination of site distributions for all transition metal cations.

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

    PubMed

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

    2017-04-19

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

  4. Surface topography and ordering-variant segregation in GaInP[sub 2

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

    Friedman, D.J.; Zhu, J.G.; Kibbler, A.E.

    1993-09-27

    Using transmission electron diffraction dark-field imaging, atomic force microscopy (AFM), and Nomarski microscopy, we demonstrate a direct connection between surface topography and cation site ordering in GaInP[sub 2]. We study epilayers grown by organometallic vapor-phase epitaxy on GaAs substrates oriented 2[degree] off (100) towards (110). Nomarski microscopy shows that, as growth proceeds, the surface of ordered material forms faceted structures aligned roughly along [011]. A comparison with the dark-field demonstrates that the [1[bar 1]1] and [11[bar 1

  5. Cation distribution correlated with magnetic properties of cobalt ferrite nanoparticles defective by vanadium doping

    NASA Astrophysics Data System (ADS)

    Heiba, Zein K.; Mohamed, Mohamed Bakr; Ahmed, S. I.

    2017-11-01

    Nanoparticles cobalt ferrite, vacancies defective through vanadium substitution for iron, were synthesized by a sol-gel method. Two systems CoFe2-xVxO4 (0.0 ≤ x ≤ 0.25) and CoFe2-1.67xVxO4 (x = 0.1, 0.2) were prepared. The crystal structure, microstructure and magnetic properties were investigated using XRD, SEM and VSM magnetometer. The occupancy of tetrahedral and octahedral sites by different cations was determined by Rietveld analysis and correlated with magnetic measurements. Vanadium resides at octahedral sites up to x = 0.10, while for higher values it resides mainly at octahedral sites with a lesser amount at the tetrahedrons. Upon increasing the vanadium content, the cell parameter decreases and the bond lengths of the tetrahedral and octahedral sites change opposite to each other. The change in the coercivity and saturation magnetization is correlated with cation distribution. For the same amount of doping x, the iron deficient samples CoFe2-1.67xVxO4 have saturation magnetization obviously reduced than the corresponding samples in CoFe2-xVxO4. The spin canting between cations in A- and B- sites was discussed in details based on Yafet-Kittel triangular arrangement model.

  6. The cooling rate dependence of cation distributions in CoFe2O4

    NASA Technical Reports Server (NTRS)

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

    1989-01-01

    The room-temperature cation distributions in bulk CoFe2O4 samples, cooled at rates between less than 0.01 and about 1000 C/sec, have been determined using Mossbauer spectroscopy in an 80-kOe magnetic field. With increasing cooling rate, the quenched structure departs increasingly from the mostly ordered cation distribution ordinarily observed at room temperature. However, the cation disorder appears to saturate just short of a random distribution at very high cooling rates. These results are interpreted in terms of a simple relaxation model of cation redistribution kinetics. The disordered cation distributions should lead to increased magnetization and decreased coercivity in CoFe2O4.

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

    PubMed

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

    2016-10-01

    The impact of pH and cations on phase behavior, stability, and surface morphology for dipalmitoylphosphatidic acid (DPPA) monolayers was investigated. At pH<10, DPPA monolayers on water are predominantly populated by neutral species and display the highest packing density. Cations are found to expand and stabilize the monolayer in the following order of increasing magnitude at pH 5.6: Na + >K + ∼Mg 2+ >Ca 2+ . Additionally, cation complexation is tied to the pH and protonation state of DPPA, which are the primary factors controlling the monolayer surface behavior. The binding affinity of cations to the headgroup and thus deprotonation capability of the cation, ranked in the order of Ca 2+ >Mg 2+ >Na + >K + , is found to be well explained by the law of matching water affinities. Nucleation of surface 3D lipid structures is observed from Ca 2+ , Mg 2+ , and Na + , but not from K + , consistent with the lowest binding affinity of K + . Unraveling cation and pH effects on DPPA monolayers is useful in further understanding the surface properties of complex systems such as organic-coated marine aerosols where organic films are directly influenced by the pH and ionic composition of the underlying aqueous phase. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  8. Cationic nanocarriers induce cell necrosis through impairment of Na+/K+-ATPase and cause subsequent inflammatory response

    PubMed Central

    Wei, Xiawei; Shao, Bin; He, Zhiyao; Ye, Tinghong; Luo, Min; Sang, Yaxiong; Liang, Xiao; Wang, Wei; Luo, Shuntao; Yang, Shengyong; Zhang, Shuang; Gong, Changyang; Gou, Maling; Deng, Hongxing; Zhao, Yinglan; Yang, Hanshuo; Deng, Senyi; Zhao, Chengjian; Yang, Li; Qian, Zhiyong; Li, Jiong; Sun, Xun; Han, Jiahuai; Jiang, Chengyu; Wu, Min; Zhang, Zhirong

    2015-01-01

    Nanocarriers with positive surface charges are known for their toxicity which has limited their clinical applications. The mechanism underlying their toxicity, such as the induction of inflammatory response, remains largely unknown. In the present study we found that injection of cationic nanocarriers, including cationic liposomes, PEI, and chitosan, led to the rapid appearance of necrotic cells. Cell necrosis induced by cationic nanocarriers is dependent on their positive surface charges, but does not require RIP1 and Mlkl. Instead, intracellular Na+ overload was found to accompany the cell death. Depletion of Na+ in culture medium or pretreatment of cells with the Na+/K+-ATPase cation-binding site inhibitor ouabain, protected cells from cell necrosis. Moreover, treatment with cationic nanocarriers inhibited Na+/K+-ATPase activity both in vitro and in vivo. The computational simulation showed that cationic carriers could interact with cation-binding site of Na+/K+-ATPase. Mice pretreated with a small dose of ouabain showed improved survival after injection of a lethal dose of cationic nanocarriers. Further analyses suggest that cell necrosis induced by cationic nanocarriers and the resulting leakage of mitochondrial DNA could trigger severe inflammation in vivo, which is mediated by a pathway involving TLR9 and MyD88 signaling. Taken together, our results reveal a novel mechanism whereby cationic nanocarriers induce acute cell necrosis through the interaction with Na+/K+-ATPase, with the subsequent exposure of mitochondrial damage-associated molecular patterns as a key event that mediates the inflammatory responses. Our study has important implications for evaluating the biocompatibility of nanocarriers and designing better and safer ones for drug delivery. PMID:25613571

  9. The cation-π interaction.

    PubMed

    Dougherty, Dennis A

    2013-04-16

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

  10. Preparation of crosslinked chitosan magnetic membrane for cations sorption from aqueous solution.

    PubMed

    Khan, Adnan; Begum, Samina; Ali, Nauman; Khan, Sabir; Hussain, Sajjad; Sotomayor, Maria Del Pilar Taboada

    2017-05-01

    A chitosan magnetic membrane was prepared in order to confer magnetic properties to the membrane, which could be used for the removal of cations from aqueous solution. The crosslinked magnetic membrane was compared with pristine chitosan membrane in term of stability, morphology and cation adsorption capacity. The fabricated magnetic materials are thermally stable as shown by thermogravimetric curves. The membrane containing nickel magnetic particles (CHNiF-G) shows high thermal stability compared to the other membranes. The Fourier transform infrared spectroscopy showed successful preparation of chitosan magnetic membrane. Scanning electron microscopy micrographs showed the rough surface of the membrane with increased porosity. The prepared chitosan membranes were applied to cations of copper, nickel and lead in dilute aqueous solution. The chitosan membrane showed the following adsorption order for metallic cations: Cu 2+ > Ni 2+ > Pb 2+ , while CHNiF-G showed higher capacity, 3.51 mmol g -1 for copper, reflecting the improvement in adsorption capacity, since the amount of copper on pristine chitosan gave 1.40 mmol g -1 . The time required for adsorption to reach to the equilibrium was 6 h for the selected cations using different chitosan membranes. The kinetic study showed that adsorption followed pseudo-second order kinetics. The most commonly used isotherm models, Freundlich, Langmuir and Temkin, were applied to experimental data using linear regression technique. However, The Temkin model fits better to experimental data.

  11. Metal cation controls phosphate release in the myosin ATPase.

    PubMed

    Ge, Jinghua; Huang, Furong; Nesmelov, Yuri E

    2017-11-01

    Myosin is an enzyme that utilizes ATP to produce a conformational change generating a force. The kinetics of the myosin reverse recovery stroke depends on the metal cation complexed with ATP. The reverse recovery stroke is slow for MgATP and fast for MnATP. The metal ion coordinates the γ phosphate of ATP in the myosin active site. It is accepted that the reverse recovery stroke is correlated with the phosphate release; therefore, magnesium "holds" phosphate tighter than manganese. Magnesium and manganese are similar ions in terms of their chemical properties and the shell complexation; hence, we propose to use these ions to study the mechanism of the phosphate release. Analysis of octahedral complexes of magnesium and manganese show that the partial charge of magnesium is higher than that of manganese and the slightly larger size of manganese ion makes its ionic potential smaller. We hypothesize that electrostatics play a role in keeping and releasing the abstracted γ phosphate in the active site, and the stronger electric charge of magnesium ion holds γ phosphate tighter. We used stable myosin-nucleotide analog complex and Raman spectroscopy to examine the effect of the metal cation on the relative position of γ phosphate analog in the active site. We found that in the manganese complex, the γ phosphate analog is 0.01 nm further away from ADP than in the magnesium complex. We conclude that the ionic potential of the metal cation plays a role in the retention of the abstracted phosphate. © 2017 The Protein Society.

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

    PubMed

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

    2011-01-28

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

  13. Atomistic understanding of cation exchange in PbS nanocrystals using simulations with pseudoligands

    PubMed Central

    Fan, Zhaochuan; Lin, Li-Chiang; Buijs, Wim; Vlugt, Thijs J. H.; van Huis, Marijn A.

    2016-01-01

    Cation exchange is a powerful tool for the synthesis of nanostructures such as core–shell nanocrystals, however, the underlying mechanism is poorly understood. Interactions of cations with ligands and solvent molecules are systematically ignored in simulations. Here, we introduce the concept of pseudoligands to incorporate cation-ligand-solvent interactions in molecular dynamics. This leads to excellent agreement with experimental data on cation exchange of PbS nanocrystals, whereby Pb ions are partially replaced by Cd ions from solution. The temperature and the ligand-type control the exchange rate and equilibrium composition of cations in the nanocrystal. Our simulations reveal that Pb ions are kicked out by exchanged Cd interstitials and migrate through interstitial sites, aided by local relaxations at core–shell interfaces and point defects. We also predict that high-pressure conditions facilitate strongly enhanced cation exchange reactions at elevated temperatures. Our approach is easily extendable to other semiconductor compounds and to other families of nanocrystals. PMID:27160371

  14. Interlaced crystals having a perfect Bravais lattice and complex chemical order revealed by real-space crystallography

    DOE PAGES

    Shen, Xiao; Hernandez-Pagan, Emil; Zhou, Wu; ...

    2014-11-14

    The search for optimal thermoelectric materials aims for structures in which the crystalline order is disrupted to lower the thermal conductivity without degradation of the electron conductivity. Here we report the synthesis and characterization of ternary nanoparticles (two cations and one anion) that exhibit a new form of crystal-line order: an uninterrupted, perfect, global Bravais lattice, in which the two cations exhibit a wide array of distinct ordering patterns within the cation sublattice, form-ing interlaced domains and phases. Partitioning into domains and phases is not unique; the corresponding boundaries have no structural defects or strain and entail no energy cost.more » We call this form of crystalline order “interlaced crystals” and present the example of hexagonal-CuInS 2. Interlacing is possible in multi-cation tetrahedral-ly-bonded compound with an average of two electrons per bond. Interlacing has min-imal effect on electronic properties, but should strongly reduce phonon transport, making interlaced crystals attractive for thermoelectric applications.« less

  15. The Cation-π Interaction

    PubMed Central

    DOUGHERTY, DENNIS A.

    2014-01-01

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

  16. Characterization of the cation-binding capacity of a potassium-adsorption filter used in red blood cell transfusion.

    PubMed

    Suzuki, Takao; Muto, Shigeaki; Miyata, Yukio; Maeda, Takao; Odate, Takayuki; Shimanaka, Kimio; Kusano, Eiji

    2015-06-01

    A K(+) -adsorption filter was developed to exchange K(+) in the supernatant of stored irradiated red blood cells with Na(+) . To date, however, the filter's adsorption capacity for K(+) has not been fully evaluated. Therefore, we characterized the cation-binding capacity of this filter. Artificial solutions containing various cations were continuously passed through the filter in 30 mL of sodium polystyrene sulfonate at 10 mL/min using an infusion pump at room temperature. The cation concentrations were measured before and during filtration. When a single solution containing K(+) , Li(+) , H(+) , Mg(2+) , Ca(2+) , or Al(3+) was continuously passed through the filter, the filter adsorbed K(+) and the other cations in exchange for Na(+) in direct proportion to the valence number. The order of affinity for cation adsorption to the filter was Ca(2+) >Mg(2+) >K(+) >H(+) >Li(+) . In K(+) -saturated conditions, the filter also adsorbed Na(+) . After complete adsorption of these cations on the filter, their concentration in the effluent increased in a sigmoidal manner over time. Cations that were bound to the filter were released if a second cation was passed through the filter, despite the different affinities of the two cations. The ability of the filter to bind cations, especially K(+) , should be helpful when it is used for red blood cell transfusion at the bedside. The filter may also be useful to gain a better understanding of the pharmacological properties of sodium polystyrene sulfonate. © 2015 The Authors. Therapeutic Apheresis and Dialysis © 2015 International Society for Apheresis.

  17. Al cation induces aggregation of serum proteins.

    PubMed

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

    2017-07-15

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

  18. Molecular field coefficients and cation distribution of substituted yttrium iron garnets

    NASA Astrophysics Data System (ADS)

    Röschmann, P.; Hansen, P.

    1981-10-01

    The saturation magnetization Ms(T) of Ga, Al, Sc, and CaVBi substituted Y3Fe5O12 (YIG) single crystals and of polycrystalline Ca/Ge and Ca/Ti substituted YIG has been investigated for 4.2 K ⩽T⩽TC. The samples were repeatedly annealed and quenched at different equilibrium temperatures 773 K⩽Te ⩽1523 K. The attained site exchange of Fe and the substituents between the a and d sites resulted in considerable changes of Ms(T). From a fit of the Néel molecular field theory to the Ms(T) data the dependence of the magnetic moments at T = 0 K and of the molecular field coefficients on the amount of nonmagnetic substitutions on the a and d sites were determined. It turned out that ion-specific sets of equations are required accounting for the ''particular ion effect'' of different cation species. The cation distributions inferred from the magnetic data have been analyzed along with a thermodynamic equilibrium model. The derived site stabilizing energies for the mixed Fe-Ga and Fe-Al garnets agree well with recently reported data. New results are presented for the site stabilizing energies in Ca/Ge:YIG and for the substituents Sc and Ti with octahedral site preference.

  19. Modifier cation effects on 29Si nuclear shielding anisotropies in silicate glasses

    NASA Astrophysics Data System (ADS)

    Baltisberger, Jay H.; Florian, Pierre; Keeler, Eric G.; Phyo, Pyae A.; Sanders, Kevin J.; Grandinetti, Philip J.

    2016-07-01

    We have examined variations in the 29Si nuclear shielding tensor parameters of SiO4 tetrahedra in a series of seven alkali and alkaline earth silicate glass compositions, Cs2O · 4.81 SiO2, Rb2O · 3.96 SiO2, Rb2O · 2.25 SiO2, K2O · 4.48 SiO2, Na2O · 4.74 SiO2, BaO · 2.64 SiO2, and SrO · 2.36 SiO2, using natural abundance 29Si two-dimensional magic-angle flipping (MAF) experiments. Our analyses of these 2D spectra reveal a linear dependence of the 29Si nuclear shielding anisotropy of Q(3) sites on the Si-non-bridging oxygen bond length, which in turn depends on the cation potential and coordination of modifier cations to the non-bridging oxygen. We also demonstrate how a combination of Cu2+ as a paramagnetic dopant combined with echo train acquisition can reduce the total experiment time of 29Si 2D NMR measurements by two orders of magnitude, enabling higher throughput 2D NMR studies of glass structure.

  20. Modifier cation effects on (29)Si nuclear shielding anisotropies in silicate glasses.

    PubMed

    Baltisberger, Jay H; Florian, Pierre; Keeler, Eric G; Phyo, Pyae A; Sanders, Kevin J; Grandinetti, Philip J

    2016-07-01

    We have examined variations in the (29)Si nuclear shielding tensor parameters of SiO4 tetrahedra in a series of seven alkali and alkaline earth silicate glass compositions, Cs2O·4.81 SiO2, Rb2O·3.96 SiO2, Rb2O·2.25 SiO2, K2O·4.48 SiO2, Na2O·4.74 SiO2, BaO·2.64 SiO2, and SrO·2.36 SiO2, using natural abundance (29)Si two-dimensional magic-angle flipping (MAF) experiments. Our analyses of these 2D spectra reveal a linear dependence of the (29)Si nuclear shielding anisotropy of Q((3)) sites on the Si-non-bridging oxygen bond length, which in turn depends on the cation potential and coordination of modifier cations to the non-bridging oxygen. We also demonstrate how a combination of Cu(2+) as a paramagnetic dopant combined with echo train acquisition can reduce the total experiment time of (29)Si 2D NMR measurements by two orders of magnitude, enabling higher throughput 2D NMR studies of glass structure. Copyright © 2016 Elsevier Inc. All rights reserved.

  1. Quantitative theory of electroosmotic flow in fused-silica capillaries using an extended site-dissociation--site-binding model.

    PubMed

    Zhou, Marilyn X; Foley, Joe P

    2006-03-15

    To optimize separations in capillary electrophoresis, it is important to control the electroosmotic mobility of the running buffer and the factors that affect it. Through the application of a site-dissociation-site-binding model, we demonstrated that the electroosmotic mobility could be controlled qualitatively and quantitatively by the parameters related to the physical and chemical properties of the running buffer: pH, cation valence, ionic strength, viscosity, activity, and dissociation constant. Our study illustrated that the logarithm of the number of apparent silanol sites on a fused-silica surface has a linear relationship with the pH of a buffer solution. The extension of the chemical kinetics approach allowed us to obtain the thickness of the electrical double layer when multivalent inorganic cations are present with monovalent cations in a buffer solution, and we found that the thickness of the electrical double layer does not depend on the charge of anions. The general equation to predict the electroosmotic mobility suggested here also indicates the increase of electroosmotic mobility with temperature. The general equation was experimentally verified by three buffer scenarios: (i) buffers containing only monovalent cations; (ii) buffers containing multivalent inorganic cations; and (iii) buffers containing cations and neutral additives. The general equation can explain the experimental observations of (i) a maximum electroosmotic mobility for the first scenario as the pH was varied at constant ionic strength and (ii) the inversion and maximum value of the electroosmotic mobility for the second scenario when the concentration of divalent cations was varied at constant pH. A good agreement between theory and experiment was obtained for each scenario.

  2. Cations Form Sequence Selective Motifs within DNA Grooves via a Combination of Cation-Pi and Ion-Dipole/Hydrogen Bond Interactions

    PubMed Central

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

    2013-01-01

    The fine conformational subtleties of DNA structure modulate many fundamental cellular processes including gene activation/repression, cellular division, and DNA repair. Most of these cellular processes rely on the conformational heterogeneity of specific DNA sequences. Factors including those structural characteristics inherent in the particular base sequence as well as those induced through interaction with solvent components combine to produce fine DNA structural variation including helical flexibility and conformation. Cation-pi interactions between solvent cations or their first hydration shell waters and the faces of DNA bases form sequence selectively and contribute to DNA structural heterogeneity. In this paper, we detect and characterize the binding patterns found in cation-pi interactions between solvent cations and DNA bases in a set of high resolution x-ray crystal structures. Specifically, we found that monovalent cations (Tl+) and the polarized first hydration shell waters of divalent cations (Mg2+, Ca2+) form cation-pi interactions with DNA bases stabilizing unstacked conformations. When these cation-pi interactions are combined with electrostatic interactions a pattern of specific binding motifs is formed within the grooves. PMID:23940752

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

    PubMed

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

    2013-01-01

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

  4. Whole-cell and single channel monovalent cation currents through the novel rabbit epithelial Ca2+ channel ECaC

    PubMed Central

    Nilius, Bernd; Vennekens, Rudi; Prenen, Jean; Hoenderop, Joost G J; Bindels, René J M; Droogmans, Guy

    2000-01-01

    This study describes properties of monovalent cation currents through ECaC, a recently cloned epithelial Ca2+-permeable channel from rabbit. The kinetics of currents through ECaC was strongly modulated by divalent cations. Currents were inhibited in the presence of extracellular Ca2+. They showed an initial voltage-dependent decay in the presence of 1 mm Mg2+ at hyperpolarizing steps in Ca2+-free solutions, which represents a voltage-dependent Mg2+ block through binding of Mg2+ to a site localized in the electrical field of the membrane (δ = 0.31) and a voltage-dependent binding constant (at 0 mV 3.1 mm Ca2+, obtained from a Woodhull type analysis). Currents were only stable in the absence of divalent cations and showed under these conditions a small time- and voltage-dependent component of activation. Single channel currents in cell-attached and inside-out patches had a conductance of 77.5 ± 4.9 pS (n = 11) and reversed at +14.8 ± 1.6 mV (n = 9) in the absence of divalent cations. The permeation sequence for monovalent cations through ECaC was Na+ > Li+ > K+ > Cs+ > NMDG+ which is identical to the Eisenmann sequence X for a strong field-strength binding site. It is concluded that the permeation profile of ECaC for monovalent cations suggests a strong field-strength binding site that may be involved in Ca2+ permeation and Mg2+ block. PMID:10970426

  5. How the cation-cation π-π stacking occurs: A theoretical investigation into ionic clusters of imidazolium.

    PubMed

    Gao, Wei; Tian, Yong; Xuan, Xiaopeng

    2015-07-01

    The cation-cation π-π stacking is uncommon but it is essential for the understanding of some supramolecular structures. We explore theoretically the nature of non-covalent interaction occurring in the stacked structure within modeled clusters of 1,3-dimethylimidazolium and halide. The evidences of the energy decomposition analysis (EDA) and reduced density gradient (RDG) approach are different from those of common π-π interaction. Isosurfaces with RDG also illustrate the strength of the titled π-π interaction and their region. Additionally, we find that the occurrence of this interaction is attributed to a few C-H···X interactions, as depicted using atom in molecule (AIM) method. This work presents a clear picture of the typical cation-cation π-π interaction and can serve to advance the understanding of this uncommon interaction. Copyright © 2015 Elsevier Inc. All rights reserved.

  6. Activation by divalent cations of a Ca2+-activated K+ channel from skeletal muscle membrane.

    PubMed

    Oberhauser, A; Alvarez, O; Latorre, R

    1988-07-01

    Several divalent cations were studied as agonists of a Ca2+-activated K+ channel obtained from rat muscle membranes and incorporated into planar lipid bilayers. The effect of these agonists on single-channel currents was tested in the absence and in the presence of Ca2+. Among the divalent cations that activate the channel, Ca2+ is the most effective, followed by Cd2+, Sr2+, Mn2+, Fe2+, and Co2+. Mg2+, Ni2+, Ba2+, Cu2+, Zn2+, Hg2+, and Sn2+ are ineffective. The voltage dependence of channel activation is the same for all the divalent cations. The time-averaged probability of the open state is a sigmoidal function of the divalent cation concentration. The sigmoidal curves are described by a dissociation constant K and a Hill coefficient N. The values of these parameters, measured at 80 mV are: N = 2.1, K = 4 X 10(-7) mMN for Ca2+; N = 3.0, K = 0.02 mMN for Cd2+; N = 1.45, K = 0.63 mMN for Sr2+; N = 1.7, K = 0.94 mMN for Mn2+; N = 1.1, K = 3.0 mMN for Fe2+; and N = 1.1 K = 4.35 mMN for Co2+. In the presence of Ca2+, the divalent cations Cd2+, Co2+, Mn2+, Ni2+, and Mg2+ are able to increase the apparent affinity of the channel for Ca2+ and they increase the Hill coefficient in a concentration-dependent fashion. These divalent cations are only effective when added to the cytoplasmic side of the channel. We suggest that these divalent cations can bind to the channel, unmasking new Ca2+ sites.

  7. Infrared Spectroscopy of Matrix-Isolated Polycyclic Aromatic Hydrocarbon Cations

    NASA Technical Reports Server (NTRS)

    Hudgins, D. M.; Allamandola, L. J.

    1995-01-01

    Gaseous, ionized polycyclic aromatic hydrocarbons (PAHs) are thought to be responsible for a very common family of interstellar infrared emission bands. Here the near- and mid-infrared spectra of the cations of the five most thermodynamically favored PAHs up to coronene: phenanthrene, pyrene, benzo(e)pyrene, benzo-(ghi)perylene, and coronene, are presented to test this hypothesis. For those molecules that have been studied previously (pyrene, pyrene-d(sub 10), and coronene), band positions and relative intensities are in agreement. In all of these cases we report additional features. Absolute integrated absorbance values are given for the phenanthrene, perdeuteriophenanthrene, pyrene, benzo(ghi]perylene, and coronene cations. With the exception of coronene, the cation bands corresponding to the CC modes are typically 2-5 times more intense than those of the CH out-of-plane bending vibrations. For the cations, the CC stretching and CH in-plane bending modes give rise to bands that are an order of magnitude stronger than those of the neutral species, and the CH out-of-plane bends produce bands that are 5-20 times weaker than those of the neutral species. This behavior is similar to that found in most other PAH cations studied to date. The astronomical implications of these PAH cation spectra are also discussed.

  8. Mg1-xZnxFe2O4 nanoparticles: Interplay between cation distribution and magnetic properties

    NASA Astrophysics Data System (ADS)

    Raghuvanshi, S.; Mazaleyrat, F.; Kane, S. N.

    2018-04-01

    Correlation between cationic distribution, magnetic properties of Mg1-xZnxFe2O4 (0.0 ≤ x ≤ 1.0) ferrite is demonstrated, hardly shown in literature. X-ray diffraction (XRD) confirms the formation of cubic spinel nano ferrites with grain diameter between 40.8 to 55.4 nm. Energy dispersive spectroscopy (EDS) confirms close agreement of Mg/Fe, Zn/Fe molar ratio, presence of all elements (Mg, Zn, Fe, O), formation of estimated ferrite composition. Zn addition (for Mg) shows: i) linear increase of lattice parameter aexp, accounted for replacement of an ion with higher ionic radius (Zn > Mg); ii) presence of higher population of Fe3+ ions on B site, and unusual occurrence of Zn, Mg on A and B site leads to non-equilibrium cation distribution where we observe inverse to mixed structure, and is in contrast to reported literature where inverse to normal transition is reported; iii) effect on A-A, A-B, B-B exchange interactions, affecting coercivity Hc, Ms. A new empirical relation is also obtained showing linear relation between saturation magnetization Ms - inversion parameter δ, oxygen parameter u4 ¯ 3 m. Non-zero Y-K angle (αYK) values implies Y-K type magnetic ordering in the studied samples.

  9. Infrared Spectroscopy of Polycyclic Aromatic Hydrocarbon Cations. 3; The Members

    NASA Technical Reports Server (NTRS)

    Hudgins, D. M.; Allamandola, L. J.; Wittebon, Fred C. (Technical Monitor)

    1994-01-01

    In spite of the fact that the infrared spectroscopic properties of only a few isolated ionized polycyclic aromatic hydrocarbons (PAHs) are known, gaseous, ionized PAHs are thought to be responsible for a very common family of infrared interstellar emission bands. In order to provide a data base to test this hypothesis and, if borne out, to use this emission band family as a probe of many different interstellar environments, we are carrying out a thorough study of the infrared spectroscopic properties of neutral and ionized PAHs in argon matrices. Here we present the near and mid-infrared spectra of the cations of the five most thermodynamically favored PAHs up to coronene: phenanthrene, pyrene, benzo[e]pyrene, benzo[ghilperylene, and coronene. The properties of naphthalene, the first member of the series, are given elsewhere. The spectra of perdeuterated phenanthrene and pyrene are also reported. For those molecules which have been previously studied (pyrene, d(10)-pyrene, and coronene), band positions and relative intensities are in agreement. In all cases we report additional features. Absolute integrated absorbance values are given for the phenanthrene, perdeutero-phenanthrene, pyrene, benzo[ghi]perylene, and coronene cations. With the exception of coronene,the cation bands corresponding to the CC modes are typically 2-5 times more intense than those of the CH out-of-plane bending vibrations. For the cations the CC stretching and CH in-plane bending modes give rise to bands which are an order of magnitude stronger than for the neutral species, and the CH out-of-plane bends produce bands which are 5-20 times weaker than in the neutral species. This behavior is similar to that found in most other PAH cations studied to date. The astronomical implications of these PAH cation spectra are also discussed.

  10. Variational first hyperpolarizabilities of 2,3-naphtho-15-crown-5 ether derivatives with cation-complexing: a potential and selective cation detector.

    PubMed

    Yu, Hai-Ling; Wang, Wen-Yong; Hong, Bo; Zong, Ying; Si, Yan-Ling; Hu, Zhong-Qiang

    2016-09-29

    Crown ethers, as a kind of heterocycle, have been the subject of great interest over recent decades due to their selective capability to bind to metal cations. The use of a constant crown ether, such as naphtho-15-crown-5 (N15C5), and varied metal cations (Li + , Na + , K + , Be 2+ , Mg 2+ , Ca 2+ , Co 2+ , Ni 2+ , Cu 2+ ) makes it possible to determine the contributions of the metal cations to nonlinear optical (NLO) responses and to design an appropriate NLO-based cation detector. N15C5 and its metal cation derivatives have been systematically investigated by density functional theory. It is found that the dependency of the first hyperpolarizability relies on the metal cation, especially for transition metals. The decrease of the first hyperpolarizabilities for alkali metal cation derivatives is due to their relatively low oscillator strengths, whereas the significant increase of the first hyperpolarizabilities for transition metal cation derivatives can be further illustrated by their low transition energies, large amplitudes and separate distributions of first hyperpolarizability density. Thus, the alkali metal and transition metal cations are distinguishable and the transition metal cations are easier to detect by utilizing the variations in NLO responses.

  11. Fluorinated Aromatic Amino Acids Distinguish Cation-π Interactions from Membrane Insertion*

    PubMed Central

    He, Tao; Gershenson, Anne; Eyles, Stephen J.; Lee, Yan-Jiun; Liu, Wenshe R.; Wang, Jiangyun; Gao, Jianmin; Roberts, Mary F.

    2015-01-01

    Cation-π interactions, where protein aromatic residues supply π systems while a positive-charged portion of phospholipid head groups are the cations, have been suggested as important binding modes for peripheral membrane proteins. However, aromatic amino acids can also insert into membranes and hydrophobically interact with lipid tails. Heretofore there has been no facile way to differentiate these two types of interactions. We show that specific incorporation of fluorinated amino acids into proteins can experimentally distinguish cation-π interactions from membrane insertion of the aromatic side chains. Fluorinated aromatic amino acids destabilize the cation-π interactions by altering electrostatics of the aromatic ring, whereas their increased hydrophobicity enhances membrane insertion. Incorporation of pentafluorophenylalanine or difluorotyrosine into a Staphylococcus aureus phosphatidylinositol-specific phospholipase C variant engineered to contain a specific PC-binding site demonstrates the effectiveness of this methodology. Applying this methodology to the plethora of tyrosine residues in Bacillus thuringiensis phosphatidylinositol-specific phospholipase C definitively identifies those involved in cation-π interactions with phosphatidylcholine. This powerful method can easily be used to determine the roles of aromatic residues in other peripheral membrane proteins and in integral membrane proteins. PMID:26092728

  12. Modeling of Substitutional Site Preference in Ordered Intermetallic Alloys

    NASA Technical Reports Server (NTRS)

    Bozzolo, Guillermo; Noebe, Ronald D.; Honecy, Frank

    1998-01-01

    We investigate the site substitution scheme of specific alloying elements in ordered compounds and the dependence of site occupancy on compound stoichiometry, alloy concentration. This basic knowledge, and the interactions with other alloying additions are necessary in order to predict and understand the effect of various alloying schemes on the physical properties of a material, its response to various temperature treatments, and the resulting mechanical properties. Many theoretical methods can provide useful but limited insight in this area, since most techniques suffer from constraints in the type of elements and the crystallographic structures that can be modeled. With this in mind, the Bozzolo-Ferrante-Smith (BFS) method for alloys was designed to overcome these limitations, with the intent of providing an useful tool for the theoretical prediction of fundamental properties and structure of complex systems. After a brief description of the BFS method, its use for the determination of site substitution schemes for individual as well as collective alloying additions to intermetallic systems is described, including results for the concentration dependence of the lattice parameter. Focusing on B2 NiAl, FeAl and CoAl alloys, the energetics of Si, Ti, V, Cr, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Hf, Ta and W alloying additions are surveyed. The effect of single additions as well as the result of two simultaneous additions, discussing the interaction between additions and their influence on site preference schemes is considered. Finally, the BFS analysis is extended to ternary L1(sub 2) (Heusler phase) alloys. A comparison between experimental and theoretical results for the limited number of cases for which experimental data is available is also included.

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

    PubMed

    Elicharova, Hana; Sychrova, Hana

    2014-08-01

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

  14. Cesium migration in Hanford sediment: a multisite cation exchange model based on laboratory transport experiments.

    PubMed

    Steefel, Carl I; Carroll, Susan; Zhao, Pihong; Roberts, Sarah

    2003-12-01

    Cs+ transport experiments carried out in columns packed with uncontaminated Hanford formation sediment from the SX tank farm provide strong support for the use of a multisite, multicomponent cation exchange model to describe Cs+ migration in the Hanford vadose zone. The experimental results indicate a strong dependence of the effective Cs+ Kd on the concentrations of other cations, including Na+ that is present at high to extremely high concentrations in fluids leaking from the Hanford SX tanks. A strong dependence of the Cs+ Kd on the aqueous Cs+ concentration is also apparent, with retardation of Cs+ increasing from a value of 41 at a Cs+ concentration of 10(-4) M in the feed solution to as much as 282 at a Cs+ concentration of 5x10(-7) M, all in a background of 1 M NaNO3. The total cation exchange capacity (CEC) of the Hanford sediment was determined using 22Na isotopic equilibrium exchange in a flow-through column experiment. The value for the CEC of 120 microeq/g determined with this method is compatible with a value of 121.9 microeq/g determined by multi-cation elution. While two distinct exchange sites were proposed by Zachara et al. [Geochim. Cosmochim. Acta 66 (2002) 193] based on binary batch exchange experiments, a third site is proposed in this study to improve the fit of the Cs+-Na+ and Cs+-Ca+ exchange data and to capture self-sharpened Cs+ breakthrough curves at low concentrations of Cs+. Two of the proposed exchange sites represent frayed edge sites (FES) on weathered micas and constitute 0.02% and 0.22% of the total CEC. Both of the FES show a very strong selectivity for Cs+ over Na+ (K(Na-Cs)=10(7.22) and 10(4.93), respectively). The third site, accounting for over 99% of the total CEC, is associated with planar sites on expansible clays and shows a smaller Na+-Cs+ selectivity coefficient of 10(1.99). Parameters derived from a fit of binary batch experiments alone tend to under predict Cs+ retardation in the column experiments. The transport

  15. Cation Uptake and Allocation by Red Pine Seedlings under Cation-Nutrient Stress in a Column Growth Experiment

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

    Shi, Zhenqing; Balogh-Brunstad, Zsuzsanna; Grant, Michael R.

    Background and Aims Plant nutrient uptake is affected by environmental stress, but how plants respond to cation-nutrient stress is poorly understood. We assessed the impact of varying degrees of cation-nutrient limitation on cation uptake in an experimental plant-mineral system. Methods Column experiments, with red pine (Pinus resinosa Ait.) seedlings growing in sand/mineral mixtures, were conducted for up to nine months under a range of Ca- and K-limited conditions. The Ca and K were supplied from both minerals and nutrient solutions with varying Ca and K concentrations. Results Cation nutrient stress had little impact on carbon allocation after nine months ofmore » plant growth and K was the limiting nutrient for biomass production. The Ca/Sr and K/Rb ratio results allowed independent estimation of dissolution incongruency and discrimination against Sr and Rb during cation uptake processes. The fraction of K in biomass from biotite increased with decreasing K supply from nutrient solutions. The mineral anorthite was consistently the major source of Ca, regardless of nutrient treatment. Conclusions Red pine seedlings exploited more mineral K in response to more severe K deficiency. This did not occur for Ca. Plant discrimination factors must be carefully considered to accurately identify nutrient sources using cation tracers.« less

  16. Cubic structure and canted antiferromagnetism of CaMn7O12 doped with trivalent cations (Fe, Al, Cr)

    NASA Astrophysics Data System (ADS)

    Motin Seikh, Md.; Caignaert, V.; Lebedev, O. I.; Raveau, B.

    2014-02-01

    In this study, we show the dramatic effect of the doping of the octahedral sites with M3+ cations (Fe3+, Al3+ and Cr3+) upon the structure and magnetism of the rhombohedral double perovskite CaMn7O12. In the oxides CaMn7-xMxO12, charge ordering between Mn3+ and Mn4+ octahedral sites is destroyed leading to the cubic structure (Im-3), whereas the initial magnetic properties (TN~90 K) have disappeared leading to canted antiferromagnetism (TN≈50-70 K) for small x values (x ~0.2-1). A spin glass like behaviour is also observed for larger values (x~1) in the case of Fe substitution.

  17. Pressure-induced cation-cation bonding in V 2 O 3

    DOE PAGES

    Bai, Ligang; Li, Quan; Corr, Serena A.; ...

    2015-10-09

    A pressure-induced phase transition, associated with the formation of cation-cation bonding, occurs in V 2O 3 by combining synchroton x-ray diffraction in a diamond anvil cell and ab initio evolutionary calculations. The high-pressure phase has a monoclinic structure with a C2/c space group, and it is both energetically and dynamically stable at pressures above 47 GPa to at least 105 GPa. this phase transition can be viewed as a two-dimensional Peierls-like distortion, where the cation-cation dimer chains are connected along the c axis of the monoclinic cell. In conclusion, this finding provides insights into the interplay of electron correlation andmore » lattice distortion in V 2O 3, and it may also help to understand novel properties of other early transition-metal oxides.« less

  18. What Hinders Electron Transfer Dissociation (ETD) of DNA Cations?

    NASA Astrophysics Data System (ADS)

    Hari, Yvonne; Leumann, Christian J.; Schürch, Stefan

    2017-12-01

    Radical activation methods, such as electron transfer dissociation (ETD), produce structural information complementary to collision-induced dissociation. Herein, electron transfer dissociation of 3-fold protonated DNA hexamers was studied to gain insight into the fragmentation mechanism. The fragmentation patterns of a large set of DNA hexamers confirm cytosine as the primary target of electron transfer. The reported data reveal backbone cleavage by internal electron transfer from the nucleobase to the phosphate linker leading either to a•/ w or d/ z• ion pairs. This reaction pathway contrasts with previous findings on the dissociation processes after electron capture by DNA cations, suggesting multiple, parallel dissociation channels. However, all these channels merely result in partial fragmentation of the precursor ion because the charge-reduced DNA radical cations are quite stable. Two hypotheses are put forward to explain the low dissociation yield of DNA radical cations: it is either attributed to non-covalent interactions between complementary fragments or to the stabilization of the unpaired electron in stacked nucleobases. MS3 experiments suggest that the charge-reduced species is the intact oligonucleotide. Moreover, introducing abasic sites significantly increases the dissociation yield of DNA cations. Consequently, the stabilization of the unpaired electron by π-π-stacking provides an appropriate rationale for the high intensity of DNA radical cations after electron transfer. [Figure not available: see fulltext.

  19. Compositional and Ionic-Size Controls on the Diffusion of Divalent Cations in Garnet: Insights from Atomistic Simulations

    NASA Astrophysics Data System (ADS)

    Carlson, W. D.

    2012-12-01

    Divalent cations in garnet (Mg, Fe, Mn, Ca) diffuse at rates that depend strongly on the host-crystal composition and on the ionic radius of the diffusant. Understanding of the nanoscale basis for these behaviors comes from atomistic simulations that calculate energies in the static limit for the defects and transition-state configurations associated with each diffusive step. Diffusion of divalent cations requires (a) creation of a cation-vacancy defect in a dodecahedral site and of a charge-compensating oxygen-vacancy defect that may or may not be in close spatial association; (b) except in the case of self-diffusion, creation of an impurity defect in which a foreign atom replaces the normal atom in a dodecahedral site adjacent to the vacancy; and (c) during the diffusive process, motion of the diffusing atom to a 'saddlepoint' position that represents the transition-state configuration. Comparisons of the system's energy in these various states, in structures of different composition and for ions of different ionic size, allows assessment of the nanoscale controls on diffusion kinetics. Molecular-statics calculations quantify defect energies and identify the transition-state configuration: the maximum energy along the diffusion path between two adjacent dodecahedral sites results when the diffusing ion is surrounded symmetrically by the six oxygen atoms that lie between the two sites. Across the range of end-member compositions, self-diffusion coefficients measured at identical conditions, and the tracer diffusivity of a single ion measured at identical conditions, can each vary by five orders of magnitude or more. Measured activation energies for these motions, however, are all equivalent to within ±6%. Calculated activation energies are in agreement with observations, in that they vary by only ±10%. Calculated vacancy-formation energies, on the other hand, are significantly larger in expanded structures; for example, that energy is greater for Prp than for

  20. Macroscopic and bulk-controlled elastic modes in an interaction of interstitial alcali metal cations within a face-centered cubic crystalline fullerine

    NASA Technical Reports Server (NTRS)

    Tatarenko, Valentine A.; Tsysman, Constantin L.; Oltarzhevskaya, Yelena T.

    1995-01-01

    The calculations in a majority of previous works for the fulleride (AqC-60) crystals were performed within the framework of the rigid-lattice model, neglecting the distortion relaxation of the host fullerene (C-60) crystal caused by the interstitial alkali-metal (A) cations. However, an each cation is a source of a static distortion field, and the resulting field is a superposition of such fields generated by all cations. This is a reason why the host-crystal distortions depend on the A-cations configurations, i.e. on a type of a spatial bulk distribution of interstitial cations. The given paper seeks to find a functional relation between the amplitudes of the doping-induced structure-distortion waves and of static concentration ones. A semiphenomenological model is constructed here within the scope of statistical-thermodynamic treatment and using the lattice-statistics simulation method(*). In this model the effects due to the presence of q solute A cations over available interstices (per unit cell) on the static inherent reorientation and/or displacements of the solvent molecules from the 'average-lattice' sites' as well as on the lattice parameter a of a elastically-anysotropic 'cubic' C-60 crystal are taken into account.

  1. Tree-Ring Cation Response to Experimental Watershed Acidification in West Virginia and Maine

    Treesearch

    David R. DeWalle; Jeffrey S. Tepp; Bryan R. Swistock; William E. Sharpe; Pamela J. Edwards

    1999-01-01

    The impact of experimental watershed acidfication on xylem cation chemistry was evaluated in eight tree species at two sites in West Virginia (Clover Run and Fernow) and one site in Maine (Bear Brook). All sites had received regular additions of (NH4) SO4 equivalent to twice the ambient annual wet plus dry atmospheric...

  2. SFG characterization of a cationic ONLO dye in biological thin films

    NASA Astrophysics Data System (ADS)

    Johnson, Lewis E.; Casford, Michael T.; Elder, Delwin L.; Davies, Paul B.; Johal, Malkiat S.

    2013-10-01

    Biopolymer-based thin films, such as those composed of CTMA-DNA, can be used as a host material for NLOactive dyes for applications such as electro-optic (EO) switching and second harmonic generation. Previous work by Heckman et al. (Proc. SPIE 6401, 640108-2) has demonstrated functioning DNA-based EO modulators. Improved performance requires optimization of both the first hyperpolarizabilities (β) and degree of acentric ordering exhibited by the chromophores. The cationic dye DANPY-1 (Proc. SPIE 8464, 846409-D) has a high affinity for DNA and a substantial hyperpolarizability; however, its macroscopic ordering has not been previously characterized. We have characterized the acentric ordering of the dye using sum-frequency generation (SFG) vibrational spectroscopy in surface-immobilized DNA and on planar metal and dielectric surfaces.

  3. Long-term tobacco plantation induces soil acidification and soil base cation loss.

    PubMed

    Zhang, Yuting; He, Xinhua; Liang, Hong; Zhao, Jian; Zhang, Yueqiang; Xu, Chen; Shi, Xiaojun

    2016-03-01

    Changes in soil exchangeable cations relative to soil acidification are less studied particularly under long-term cash crop plantation. This study investigated soil acidification in an Ali-Periudic Argosols after 10-year (2002-2012) long-term continuous tobacco plantation. Soils were respectively sampled at 1933 and 2143 sites in 2002 and 2012 (also 647 tobacco plants), from seven tobacco plantation counties in the Chongqing Municipal City, southwest China. After 10-year continuous tobacco plantation, a substantial acidification was evidenced by an average decrease of 0.20 soil pH unit with a substantial increase of soil sites toward the acidic status, especially those pH ranging from 4.5 to 5.5, whereas 1.93 kmol H(+) production ha(-1) year(-1) was mostly derived from nitrogen (N) fertilizer input and plant N uptake output. After 1 decade, an average decrease of 27.6 % total exchangeable base cations or of 0.20 pH unit occurred in all seven tobacco plantation counties. Meanwhile, for one unit pH decrease, 40.3 and 28.3 mmol base cations kg(-1) soil were consumed in 2002 and 2012, respectively. Furthermore, the aboveground tobacco biomass harvest removed 339.23 kg base cations ha(-1) year(-1) from soil, which was 7.57 times higher than the anions removal, leading to a 12.52 kmol H(+) production ha(-1) year(-1) as the main reason inducing soil acidification. Overall, our results showed that long-term tobacco plantation not only stimulated soil acidification but also decreased soil acid-buffering capacity, resulting in negative effects on sustainable soil uses. On the other hand, our results addressed the importance of a continuous monitoring of soil pH changes in tobacco plantation sites, which would enhance our understanding of soil fertility of health in this region.

  4. Cation distribution, magnetic properties and cubic-perovskite phase transition in bismuth-doped nickel ferrite

    NASA Astrophysics Data System (ADS)

    Gore, Shyam K.; Jadhav, Santosh S.; Tumberphale, Umakant B.; Shaikh, Shoyeb M.; Naushad, Mu; Mane, Rajaram S.

    2017-12-01

    The phase transition of bismuth-substituted nickel ferrite, synthesized by using a simple sol-gel autocombustion method, from cubic to perovskite is confirmed from the X-ray diffraction spectrums. The changes in isomer shift, hyperfine field and cation distribution are obtained from the Mossbauer spectroscopy analysis. The cation distribution demonstrates Ni2+ cations occupy tetrahedral sites, while Fe3+ and Bi3+ occupy both tetrahedral as well as octahedral sites. For higher concentrations of bismuth, saturation magnetization is increased whereas, coercivity is decreased which is related to phase change. The variations of dielectric constant, tangent loss and conductivity (ac) with frequency (10 Hz-5 MHz) have been explored with Bi3+-doping i.e. 'x'. According to Maxwell-Wagener model, there is an involvement of electron hopping kinetics as both dielectric constant and tangent loss are decreased with increasing frequency. Increase of conductivity with frequency (measured at room temperature, 27 °C) is attributed to increase of number of carriers and mobility.

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

    PubMed

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

    2018-04-25

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

  6. The C4H7+ cation. A theoretical investigation

    NASA Technical Reports Server (NTRS)

    Koch, W.; Liu, B.; DeFrees, D. J.

    1988-01-01

    The potential energy surface of the C4H7+ cation has been investigated with ab initio quantum chemical theory. Extended basis set calculations, including electronic correlation, show that cyclobutyl and cyclopropylcarbinyl cation are equally stable isomers. The saddle point connecting these isomers lies 0.6 kcal/mol above the minima. The global C4H7+ minimum corresponds to the 1-methylallyl cation, which is 9.0 kcal/mol more stable than the cyclobutyl and the cyclopropylcarbinyl cation and 9.5 kcal/mol below the 2-methylallyl cation. These results are in excellent agreement with experimental data.

  7. X-ray diffraction and Mössbauer spectroscopy studies of LiFe 0.5Ti 1.5O 4 - A new primitive cubic ordered spinel

    NASA Astrophysics Data System (ADS)

    Avdeev, Georgi; Petrov, Kostadin; Mitov, Ivan

    2007-12-01

    LiFe 0.5Ti 1.5O 4 was synthesized by solid-state reaction carried out at 900 °C in flowing argon atmosphere, followed by rapid quenching of the reaction product to room temperature. The compound has been characterized by X-ray powder diffraction (XRD) and 57Fe Mössbauer effect spectroscopy (MES). It crystallizes in the space group P4 332, a = 8.4048(1) Å. Results from Rietveld structural refinement indicated 1:3 cation ordering on the octahedral sites: Li occupies the octahedral (4 b) sites, Ti occupies the octahedral (12 d) sites, while the tetrahedral (8 c) sites have mixed (Fe/Li) occupancy. A small, about 5%, inversion of Fe on the (4 b) sites has been detected. The MES data is consistent with cation distribution and oxidation state of Fe, determined from the structural data. The title compound is thermally unstable in air atmosphere. At 800 °C it transforms to a mixture of two Fe 3+ containing phases - a face centred cubic spinel Li (1+ y)/2 Fe (5-3 y)/2 Ti yO 4 and a Li ( z-1)/2 Fe (7-3 z)/2 Ti zO 5 - pseudobrookite. The major product of thermal treatment at 1000 °C is a ramsdellite type lithium titanium iron(III) oxide, accompanied by traces of rutile and pseudobrookite.

  8. A-Site Cation Substitutions in Strained Y-Doped BaZrO 3 Multilayer Films Leading to Fast Proton Transport Pathways

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

    Aruta, Carmela; Han, Chu; Zhou, Si

    Proton-conducting perovskite oxides form a class of solid electrolytes for novel electrochemical devices operating at moderate temperatures. Here, we use hard X-ray photoelectron spectroscopy, scanning transmission electron microscopy, and density functional theory calculations to investigate the structure and elucidate the origin of the fast proton transport properties of strained ultrathin films of Y-doped BaZrO 3 grown by pulsed lased deposition on NdGaO 3. Our study shows that our BaZr 0.8Y 0.2O 3 films incorporate a significant amount of Y dopants, and to a lesser extent also Zr ions, substituting for Ba 2+, and that these substitutional defects agglomerate forming columnarmore » regions crossing vertically from the surface to the interface the entire film. In conclusion, our calculations also show that, in regions rich in Y substitutions for both Zr and Ba, the proton transfer process involves nearly zero-energy barriers, indicating that A-site cation substitutions by Y lead to fast transport pathways and hence are responsible for the previously observed enhanced values of the proton conductivity of these perovskite oxide films.« less

  9. Cation-Inhibited Transport of Graphene Oxide Nanomaterials in Saturated Porous Media: The Hofmeister Effects.

    PubMed

    Xia, Tianjiao; Qi, Yu; Liu, Jing; Qi, Zhichong; Chen, Wei; Wiesner, Mark R

    2017-01-17

    Transport of negatively charged nanoparticles in porous media is largely affected by cations. To date, little is known about how cations of the same valence may affect nanoparticle transport differently. We observed that the effects of cations on the transport of graphene oxide (GO) and sulfide-reduced GO (RGO) in saturated quartz sand obeyed the Hofmeister series; that is, transport-inhibition effects of alkali metal ions followed the order of Na + < K + < Cs + , and those of alkaline earth metal ions followed the order of Mg 2+ < Ca 2+ < Ba 2+ . With batch adsorption experiments and microscopic data, we verified that cations having large ionic radii (and thus being weakly hydrated) interacted with quartz sand and GO and RGO more strongly than did cations of small ionic radii. In particular, the monovalent Cs + and divalent Ca 2+ and Ba 2+ , which can form inner-sphere complexes, resulted in very significant deposition of GO and RGO via cation bridging between quartz sand and GO and RGO, and possibly via enhanced straining, due to the enhanced aggregation of GO and RGO from cation bridging. The existence of the Hofmeister effects was further corroborated with the interesting observation that cation bridging was more significant for RGO, which contained greater amounts of carboxyl and phenolic groups (i.e., metal-complexing moieties) than did GO. The findings further demonstrate that transport of nanoparticles is controlled by the complex interplay between nanoparticle surface functionalities and solution chemistry constituents.

  10. Abundances of volatile-bearing phases in carbonaceous chondrites and cooling rates of meteorites based on cation ordering of orthopyroxenes

    NASA Technical Reports Server (NTRS)

    Ganguly, Jibamitra

    1989-01-01

    Results of preliminary calculations of volatile abundances in carbonaceous chondrites are discussed. The method (Ganguly 1982) was refined for the calculation of cooling rate on the basis of cation ordering in orthopyroxenes, and it was applied to the derivation of cooling rates of some stony meteorites. Evaluation of cooling rate is important to the analysis of condensation, accretion, and post-accretionary metamorphic histories of meteorites. The method of orthopyroxene speedometry is widely applicable to meteorites and would be very useful in the understanding of the evolutionary histories of carbonaceous chondrites, especially since the conventional metallographic and fission track methods yield widely different results in many cases. Abstracts are given which summarize the major conclusions of the volatile abundance and cooling rate calculations.

  11. Thermally Activated Motion of Sodium Cations in Insulating Parent Low-Silica X Zeolite

    NASA Astrophysics Data System (ADS)

    Igarashi, Mutsuo; Jeglič, Peter; Mežnaršič, Tadej; Nakano, Takehito; Nozue, Yasuo; Watanabe, Naohiro; Arčon, Denis

    2017-07-01

    We report a 23Na spin-lattice relaxation rate, T1 - 1, in low-silica X zeolite. T1 - 1 follows multiple BPP-type behavior as a result of thermal motion of sodium cations in insulating material. The estimated lowest activation energy of 15 meV is much lower than 100 meV observed previously for sodium motion in heavily Na-loaded samples and is most likely attributed to short-distance jumps of sodium cations between sites within the same supercage.

  12. Influence of acidic eluent for retention behaviors of common anions and cations by ion-exclusion/cation-exchange chromatography on a weakly acidic cation-exchange resin in the H+ -form.

    PubMed

    Mori, Masanobu; Tanaka, Kazuhiko; Satori, Tatsuya; Ikedo, Mikaru; Hu, Wenzhi; Itabashi, Hideyuki

    2006-06-16

    Influence of acidic eluent on retention behaviors of common anions and cations by ion-exclusion/cation-exchange chromatography (ion-exclusion/CEC) were investigated on a weakly acidic cation-exchange resin in the H(+)-form with conductivity. Sensitivities of analyte ions, especially weak acid anions (F(-) and HCOO(-)), were affected with degree of background conductivity level with pK(a1) (first dissociation constant) of acid in eluent. The retention behaviors of anions and cations were related to that of elution dip induced after eluting acid to separation column and injecting analyte sample. These results were largely dependent on the natures of acid as eluent. Through this study, succinic acid as the eluent was suitable for simultaneous separation of strong acid anions (SO(4)(2-), Cl(-), NO(3)(-) and I(-)), weak acid anions (F(-), HCOO(-) and CH(3)COO(-)), and cations (Na(+), K(+), NH(4)(+), Mg(2+) and Ca(2+)). The separation was achieved in 20 min under the optimum eluent condition, 20 mM succinic acid/2 mM 18-crown-6. Detection limits at S/N=3 ranged from 0.10 to 0.51 microM for strong acid anions, 0.20 to 5.04 microM for weak acid anions and 0.75 to 1.72 microM for cations. The relative standard deviations of peak areas in the repeated chromatographic runs (n=10) were in the range of 1.1-2.9% for anions and 1.8-4.5% for cations. This method was successfully applied to hot spring water containing strong acid anions, weak acid anions and cations, with satisfactory results.

  13. Cation Binding to Xanthorhodopsin: Electron Paramagnetic Resonance and Magnetic Studies.

    PubMed

    Smolensky Koganov, Elena; Leitus, Gregory; Rozin, Rinat; Weiner, Lev; Friedman, Noga; Sheves, Mordechai

    2017-05-04

    Xanthorhodopsin (xR) is a member of the retinal protein family and acts as a proton pump in the cell membranes of the extremely halophilic eubacterium Salinibacter ruber. In addition to the retinal chromophore, xR contains a carotenoid, which acts as a light-harvesting antenna as it transfers 40% of the quanta it absorbs to the retinal. Our previous studies have shown that the CD and absorption spectra of xR are dramatically affected due to the protonation of two different residues. It is still unclear whether xR can bind cations. Electron paramagnetic resonance (EPR) spectroscopy used in the present study revealed that xR can bind divalent cations, such as Mn 2+ and Ca 2+ , to deionized xR (DI-xR). We also demonstrate that xR can bind 1 equiv of Mn 2+ to a high-affinity binding site followed by binding of ∼40 equiv in cooperative manner and ∼100 equiv of Mn 2+ that are weakly bound. SQUID magnetic studies suggest that the high cooperative binding of Mn 2+ cations to xR is due to the formation of Mn 2+ clusters. Our data demonstrate that Ca 2+ cations bind to DI-xR with a lower affinity than Mn 2+ , supporting the assumption that binding of Mn 2+ occurs through cluster formation, because Ca 2+ cations cannot form clusters in contrast to Mn 2+ .

  14. Determinants of cation transport selectivity: Equilibrium binding and transport kinetics

    PubMed Central

    2015-01-01

    The crystal structures of channels and transporters reveal the chemical nature of ion-binding sites and, thereby, constrain mechanistic models for their transport processes. However, these structures, in and of themselves, do not reveal equilibrium selectivity or transport preferences, which can be discerned only from various functional assays. In this Review, I explore the relationship between cation transport protein structures, equilibrium binding measurements, and ion transport selectivity. The primary focus is on K+-selective channels and nonselective cation channels because they have been extensively studied both functionally and structurally, but the principles discussed are relevant to other transport proteins and molecules. PMID:26078056

  15. Experimental and theoretical study using DFT method for the competitive adsorption of two cationic dyes from wastewaters

    NASA Astrophysics Data System (ADS)

    Regti, Abdelmajid; Ayouchia, Hicham Ben El; Laamari, My Rachid; Stiriba, Salah Eddine; Anane, Hafid; Haddad, Mohammadine El

    2016-12-01

    The adsorption of cationic dyes, Basic Yellow (BY28) and Methylene Blue (MB) on a new activated carbon from medlar species were studied in both single and binary system. Some experimental parameters, namely, pH, amount of adsorbent and contact time are studied. Quantum chemical results indicate that the adsorption efficiency was directly related to the dye electrophilicity power. Some theorical parameters were calculated and proved that MB is more electrophilic than BY28, than greatest interaction with surface sites. Kinetic study showed that the adsorption follows the pseudo-second-order model and Freundlich was the best model to describe the phenomenon in the single and binary system. According to the local reactivity results using Parr functions, the sulphur and nitrogen atoms will be the main adsorption sites.

  16. Claudin-2-mediated cation and water transport share a common pore

    PubMed Central

    Rosenthal, Rita; Günzel, Dorothee; Krug, Susanne M.; Schulzke, Jörg-Dieter; Fromm, Michael; Yu, Alan S.L.

    2016-01-01

    Aim Claudin-2 is a tight junction protein typically located in “leaky” epithelia exhibiting large paracellular permeabilities like small intestine and proximal kidney tubule. Former studies revealed that claudin-2 forms paracellular channels for small cations like sodium and potassium and also paracellular channels for water. This study analyzes whether the diffusive transport of sodium and water occurs through a common pore of the claudin-2 channel. Methods Wild-type claudin-2 and different claudin-2 mutants were expressed in MDCK I kidney tubule cells using an inducible system. Ion and water permeability and the effect of blocking reagents on both were investigated on different clones of the mutants. Results Neutralization of a negatively charged cation interaction site in the pore with the mutation, D65N, decreased both, sodium permeability and water permeability. Claudin-2 mutants (I66C and S68C) with substitution of the pore-lining amino acids with cysteine were used to test the effect of steric blocking of the claudin-2 pore by thiol-reactive reagents. Addition of thiol-reactive reagents to these mutants simultaneously decreased conductance and water permeability. Remarkably, all experimental perturbations caused parallel changes in ion conductance and water permeability, disproving different or independent passage pathways. Conclusion Our results indicate that claudin-2-mediated cation and water transport are frictionally coupled and share a common pore. This pore is lined and determined in permeability by amino acid residues of the first extracellular loop of claudin-2. PMID:27359349

  17. Macroscopic and bulk-controlled elastic modes in an interaction of interstitial alcali metal cations within a face-centered cubic crystalline fullerine

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

    Tatarenko, V.A.; Tsysman, C.L.; Oltarzhevskaya, Y.T.

    1994-12-31

    The calculations in a majority of previous works for the fulleride (AqC{sub 60}) crystals were performed within the framework of the rigid-lattice model, neglecting the distoration relaxation of the host fullerene (C{sub 60}) crystal caused by the interstitial alkali-metal (A) cations. However, an each cation is a source of a static distoration field, and the resulting field is a superposition of such fields generated by all cations. This is a reason why the host-crystal distortions depend on the A-cations configurations, i.e. on a type of a spatial bulk distribution of interstitial cations. This paper seeks to find a functional relationmore » between the amplitudes of the doping-induced structure-distortion waves and of statistic concentration ones. A semiphenomenological model is constructed here within the scope of statistical-thermodynamic treatment and using the lattice-statistics simulation method. In this model the effects due to the presence of q solute A cations over available interstices (per unit cell) on the statistic inherent reorientation and/or displacements of the solvent molecules from the average-lattice sites as well as on the lattice parameter a of the elastically-anysotropic cubic C{sub 60} crystal are taken into account.« less

  18. Spin structure, magnetism, and cation distributions of NiFe2-xAlxO4 solid solutions

    NASA Astrophysics Data System (ADS)

    Kamali, Saeed

    2017-07-01

    Low temperature Mössbauer spectroscopy together with isothermal magnetization and zero-field-cooled and field-cooled measurements have been used to perform a systematic investigation of the cation distributions and magnetic properties of solid solutions of NiFe2-xAlxO4 with x = 0.0, 0.4, 0.8, 1.2, 1.6, and 2.0. Mössbauer spectroscopy for the starting member of the series, NiFe2O4, shows that nickel atoms occupy the octahedral sites and are in 2+ oxidation state, while iron atoms, all in 3+ oxidation state, occupy equally the tetrahedral and the octahedral sites. When low concentration of aluminum, x = 0.4, is incorporated into the system, they substitute preferentially iron atoms in the octahedral sites. As the concentration of aluminum is increased, there are distributions of them in both the tetrahedral and octahedral sites leading to complex cation distributions. The magnetic characters of iron and nickel atoms and the diamagnetic nature of aluminum atoms and the complex cation distributions result in interesting magnetic properties for this class of materials. As the concentration of aluminum increases, the saturation magnetization decreases drastically and then gradually increases. In the end member of the series, NiAl2O4, the absent of any super-exchange interaction between the A-sites and the B-sites due to presence of Ni ions as the only magnetic atoms in the B-sites results in a paramagnetic structure and a magnetization close to zero although the nickel atoms have a spin moment of 2μB . This paramagnetic feature makes this compound to be considered as a magnetic resonant imaging agent. Another very interesting feature is the back and forth switching of the dominance of the magnetic moments in the tetrahedral sites and the octahedral sites as aluminum concentration increases.

  19. Employment of cationic solid-lipid nanoparticles as RNA carriers.

    PubMed

    Montana, Giovanna; Bondì, Maria L; Carrotta, Rita; Picone, Pasquale; Craparo, Emanuela F; San Biagio, Pier L; Giammona, Gaetano; Di Carlo, Marta

    2007-01-01

    Gene transfer represents an important advance in the treatment of both genetic and acquired diseases. In this article, the suitability of cationically modified solid-lipid nanoparticles (SLN) as a nonviral vector for gene delivery was investigated, in order to obtain stable materials able to condense RNA. Cationic SLN were produced by microemulsion using Compritol ATO 888 as matrix lipid, Pluronic F68 as tenside, and dimethyldioctadecylammonium bromide (DDAB) as cationic lipid. The resulting particles were approximately 100 nm in size and showed a highly positive surface charge (+41 mV) in water. Size and shape were further characterized by scanning electron microscopy (SEM) measurements. Moreover, we utilized the sea urchin as a model system to test their applicability on a living organism. To evaluate cationic SLN ability to complex the in vitro transcribed Paracentrotus lividus bep3 RNA, we utilized both light scattering and gel mobility experiments, and protection by nuclease degradation was also investigated. By microinjection experiment, we demonstrated that the nanoparticles do not inference with the viability of the P. lividus embryo and the complex nanoparticles-bep3 permits movement of the RNA during its localization in the egg, suggesting that it could be a suitable system for gene delivery. Taken together, all these results indicate that the cationic SNL are a good RNA carrier for gene transfer system and the sea urchin a simple and versatile candidate to test biological properties of nanotechnology devices.

  20. Structure and ionic diffusion of alkaline-earth ions in mixed cation glasses A 2O–2MO–4SiO 2 with molecular dynamics simulations

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

    Konstantinou, Konstantinos; Sushko, Petr; Duffy, Dorothy M.

    2015-05-15

    A series of mixed cation silicate glasses of the composition A2O – 2MO – 4SiO2, with A=Li,Na,K and M=Ca,Sr,Ba has been investigated by means of molecular dynamics simulations in order to understand the effect of the nature of the cations on the mobility of the alkaline-earth ions within the glass network. The size of the alkaline-earth cation was found to affect the inter-atomic distances, the coordination number distributions and the bond angle distributions , whereas the medium-range order was almost unaffected by the type of the cation. All the alkaline-earth cations contribute to lower vibrational frequencies but it is observedmore » that that there is a shift to smaller frequencies and the vibrational density of states distribution gets narrower as the size of the alkaline-earth increases. The results from our modeling for the ionic diffusion of the alkaline-earth cations are in a qualitative agreement with the experimental observations in that there is a distinct correlation between the activation energy for diffusion of alkaline earth-ions and the cation radii ratio. An asymmetrical linear behavior in the diffusion activation energy with increasing size difference is observed. The results can be described on the basis of a theoretical model that relates the diffusion activation energy to the electrostatic interactions of the cations with the oxygens and the elastic deformation of the silicate network.« less

  1. Raft membrane domains: from a liquid-ordered membrane phase to a site of pathogen attack.

    PubMed

    van der Goot, F G; Harder, T

    2001-04-01

    While the existence of cholesterol/sphingolipid (raft) membrane domains in the plasma membrane is now supported by strong experimental evidence, the structure of these domains, their size, their dynamics, and their molecular composition remain to be understood. Raft domains are thought to represent a specific physical state of lipid bilayers, the liquid-ordered phase. Recent observations suggest that in the mammalian plasma membrane small raft domains in ordered lipid phases are in a dynamic equilibrium with a less ordered membrane environment. Rafts may be enlarged and/or stabilized by protein-mediated cross-linking of raft-associated components. These changes of plasma membrane structure are perceived by the cells as signals, most likely an important element of immunoreceptor signalling. Pathogens abuse raft domains on the host cell plasma membrane as concentration devices, as signalling platforms and/or entry sites into the cell. Elucidation of these interactions requires a detailed understanding raft structure and dynamics. Copyright 2001 Academic Press.

  2. Density-Functional-Theory Modeling of Cation Diffusion in Bulk La 1 - x Sr x MnO 3 ± δ ( x = 0.0 – 0.25 ) for Solid-Oxide Fuel-Cell Cathodes

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

    Lee, Yueh-Lin; Duan, Yuhua; Morgan, Dane

    In this work, the A - and B -site cation migration pathways involving defect complexes in bulk La 1-xSr xMnO 3±δ (LSM) at x = 0.0-0.25 are investigated based on density-functional-theory modeling for solid-oxide fuel-cell (SOFC) cathode applications. We propose a dominant A -site cation migration mechanism which involves an A -site cation (e.g., Lamore » $$x\\atop{A}$$) V A"' of a V A"' -V B"' cluster, where La$$x\\atop{A}$$, V A"' and V B"' are La 3+, A-site vacancy, and B-site vacancy in bulk LSM, respectively, and V A"' -V B"' is the first nearest-neighbor V A"' and V B"' pair. This hop exhibits an approximately 1.6-eV migration barrier as compared to approximately 2.9 eV of the La$$x\\atop{A}$$ hop into a V A"'. This decrease in the cation migration barrier is attributed to the presence of the V B"' relieving the electrostatic repulsion and steric constraints to the migrating A-site cations in the transition-state image configurations.« less

  3. Density-Functional-Theory Modeling of Cation Diffusion in Bulk La 1 - x Sr x MnO 3 ± δ ( x = 0.0 – 0.25 ) for Solid-Oxide Fuel-Cell Cathodes

    DOE PAGES

    Lee, Yueh-Lin; Duan, Yuhua; Morgan, Dane; ...

    2017-10-04

    In this work, the A - and B -site cation migration pathways involving defect complexes in bulk La 1-xSr xMnO 3±δ (LSM) at x = 0.0-0.25 are investigated based on density-functional-theory modeling for solid-oxide fuel-cell (SOFC) cathode applications. We propose a dominant A -site cation migration mechanism which involves an A -site cation (e.g., Lamore » $$x\\atop{A}$$) V A"' of a V A"' -V B"' cluster, where La$$x\\atop{A}$$, V A"' and V B"' are La 3+, A-site vacancy, and B-site vacancy in bulk LSM, respectively, and V A"' -V B"' is the first nearest-neighbor V A"' and V B"' pair. This hop exhibits an approximately 1.6-eV migration barrier as compared to approximately 2.9 eV of the La$$x\\atop{A}$$ hop into a V A"'. This decrease in the cation migration barrier is attributed to the presence of the V B"' relieving the electrostatic repulsion and steric constraints to the migrating A-site cations in the transition-state image configurations.« less

  4. Cation Ordering in Li[NixMnxCo(1-2x)]O2-Layered Cathode Materials: A Nuclear Magnetic Resonance (NMR), Pair Distribution Function, X-ray Absorption Spectroscopy, and Electrochemical Study

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

    Zeng,D.; Cabana, J.; Breger, J.

    2007-01-01

    Several members of the compositional series Li[NixMnxCo(1-2x)]O2 (0.01 = x = 1/3) were synthesized and characterized. X-ray diffraction results confirm the presence of the layered a-NaFeO2-type structure, while X-ray absorption near-edge spectroscopy experiments verify the presence of Ni2+, Mn4+, and Co3+. Their local environment and short-range ordering were investigated by using a combination of 6Li magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and neutron pair distribution function (PDF) analysis, associated with reverse Monte Carlo (RMC) calculations. The 6Li MAS NMR spectra of compounds with low Ni/Mn contents (x = 0.10) show several well-resolved resonances, which start to mergemore » when the amount of Ni and Mn increases, finally forming a broad resonance at high Ni/Mn contents. Analysis of the 6Li MAS NMR 6Li[Ni0.02Mn0.02Co0.96]O2 spectrum, is consistent with the formation of Ni2+ and Mn4+ clusters within the transition-metal layers, even at these low-doping levels. The oxidation state of Ni in this high Co content sample strongly depends upon the Li/transition metal ratio of the starting materials. Neutron PDF analysis of the highest Ni/Mn content sample Li[Ni1/3Mn1/3Co1/3]O2 shows a tendency for Ni cations to be close to Mn cations in the first coordination shell; however, the Co3+ ions are randomly distributed. Analysis of the intensity of the 'LiCoO2' resonance, arising from Li surrounded by Co3+ in its first two cation coordination shells, for the whole series provides further evidence for a nonrandom distribution of the transition-metal cations. The presence of the insulator-to-metal transition seen in the electrochemical profiles of these materials upon charging correlates strongly with the concentration of the 'LiCoO2' resonance.« less

  5. Unmasking tandem site interaction in human acetylcholinesterase. Substrate activation with a cationic acetanilide substrate.

    PubMed

    Johnson, Joseph L; Cusack, Bernadette; Davies, Matthew P; Fauq, Abdul; Rosenberry, Terrone L

    2003-05-13

    Acetylcholinesterase (AChE) contains a narrow and deep active site gorge with two sites of ligand binding, an acylation site (or A-site) at the base of the gorge, and a peripheral site (or P-site) near the gorge entrance. The P-site contributes to catalytic efficiency by transiently binding substrates on their way to the acylation site, where a short-lived acyl enzyme intermediate is produced. A conformational interaction between the A- and P-sites has recently been found to modulate ligand affinities. We now demonstrate that this interaction is of functional importance by showing that the acetylation rate constant of a substrate bound to the A-site is increased by a factor a when a second molecule of substrate binds to the P-site. This demonstration became feasible through the introduction of a new acetanilide substrate analogue of acetylcholine, 3-(acetamido)-N,N,N-trimethylanilinium (ATMA), for which a = 4. This substrate has a low acetylation rate constant and equilibrates with the catalytic site, allowing a tractable algebraic solution to the rate equation for substrate hydrolysis. ATMA affinities for the A- and P-sites deduced from the kinetic analysis were confirmed by fluorescence titration with thioflavin T as a reporter ligand. Values of a >1 give rise to a hydrolysis profile called substrate activation, and the AChE site-specific mutant W86F, and to a lesser extent wild-type human AChE itself, showed substrate activation with acetylthiocholine as the substrate. Substrate activation was incorporated into a previous catalytic scheme for AChE in which a bound P-site ligand can also block product dissociation from the A-site, and two additional features of the AChE catalytic pathway were revealed. First, the ability of a bound P-site ligand to increase the substrate acetylation rate constant varied with the structure of the ligand: thioflavin T accelerated ATMA acetylation by a factor a(2) of 1.3, while propidium failed to accelerate. Second, catalytic rate

  6. Method for encapsulating and isolating hazardous cations, medium for encapsulating and isolating hazardous cations

    DOEpatents

    Wasserman, S.R.; Anderson, K.B.; Song, K.; Yuchs, S.E.; Marshall, C.L.

    1998-04-28

    A method for encapsulating hazardous cations is provided comprising supplying a pretreated substrate containing the cations; contacting the substrate with an organo-silane compound to form a coating on the substrate; and allowing the coating to cure. A medium for containing hazardous cations is also provided, comprising a substrate having ion-exchange capacity and a silane-containing coating on the substrate. 3 figs.

  7. Inversion of membrane surface charge by trivalent cations probed with a cation-selective channel

    PubMed Central

    Gurnev, Philip A.; Bezrukov, Sergey M.

    2014-01-01

    We demonstrate that the cation-selective channel formed by gramicidin A can be used as a reliable sensor for studying the multivalent ion accumulation at the surfaces of charged lipid membranes and the “charge inversion” phenomenon. In asymmetrically charged membranes with the individual leaflets formed from pure negative and positive lipids bathed by 0.1 M CsCl solutions the channel exhibits current rectification which is comparable to that of a typical n/p semiconductor diode. We show that even at these highly asymmetrical conditions the channel conductance can be satisfactorily described by the electrodiffusion equation in the constant field approximation but, due to predictable limitations, only when the applied voltages do not exceed 50 mV. Analysis of the changes in the voltage-dependent channel conductance upon addition of trivalent cations allows us to gauge their interactions with the membrane surface. The inversion of the sign of the effective surface charge takes place at the concentrations which correlate with the cation size. Specifically, these concentrations are close to 0.05 mM for lanthanum, 0.25 mM for hexaamminecobalt, and 4 mM for spermidine. PMID:23088396

  8. Inversion of membrane surface charge by trivalent cations probed with a cation-selective channel.

    PubMed

    Gurnev, Philip A; Bezrukov, Sergey M

    2012-11-13

    We demonstrate that the cation-selective channel formed by gramicidin A can be used as a reliable sensor for studying the multivalent ion accumulation at the surfaces of charged lipid membranes and the "charge inversion" phenomenon. In asymmetrically charged membranes with the individual leaflets formed from pure negative and positive lipids bathed by 0.1 M CsCl solutions the channel exhibits current rectification, which is comparable to that of a typical n/p semiconductor diode. We show that even at these highly asymmetrical conditions the channel conductance can be satisfactorily described by the electrodiffusion equation in the constant field approximation but, due to predictable limitations, only when the applied voltages do not exceed 50 mV. Analysis of the changes in the voltage-dependent channel conductance upon addition of trivalent cations allows us to gauge their interactions with the membrane surface. The inversion of the sign of the effective surface charge takes place at the concentrations, which correlate with the cation size. Specifically, these concentrations are close to 0.05 mM for lanthanum, 0.25 mM for hexaamminecobalt, and 4 mM for spermidine.

  9. Trivalent Lewis Acidic Cations Govern the Electronic Properties and Stability of Heterobimetallic Complexes of Nickel.

    PubMed

    Kumar, Amit; Lionetti, Davide; Day, Victor W; Blakemore, James D

    2018-01-02

    Assembly of heterobimetallic complexes is synthetically challenging due to the propensity of ditopic ligands to bind metals unselectively. Here, we employ a novel divergent approach for selective preparation of a variety of bimetallic complexes within a ditopic macrocyclic ligand platform. In our approach, nickel is readily coordinated to a Schiff base cavity, and then a range of redox-inactive cations (M=Na + , Ca 2+ , Nd 3+ , and Y 3+ ) are installed in a pendant crown-ether-like site. This modular strategy allows access to complexes with the highly Lewis acidic trivalent cations Nd 3+ and Y 3+ , a class of compounds that were previously inaccessible. Spectroscopic and electrochemical studies reveal wide variations in properties that are governed most strongly by the trivalent cations. Exposure to dimethylformamide drives loss of Nd 3+ and Y 3+ from the pendant crown-ether site, suggesting solvent effects must be carefully considered in future applications involving use of highly Lewis acidic metals. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. A-site Ordered Chromium Perovskites, ACu3Cr4O12 with A = Trivalent Ions

    NASA Astrophysics Data System (ADS)

    Sugiyama, Jun; Nozaki, Hiroshi; Umegaki, Izumi; Higemoto, Wataru; Isobe, Masahiko; Takagi, Hidenori; Sakurai, Hiroya; Ansaldo, Eduardo J.; Brewer, Jess H.; Sassa, Yasmine; Forslund, Ola Kenji; Månsson, Martin

    The magnetic ground state of the A-site ordered chromium perovskites, ACu3Cr4O12 with A = Y, La, Eu, and Lu has been investigated with μ+SR using powder samples prepared by a high-pressure technique. Weak transverse field measurements revealed that the four compounds enter into a magnetic phase below 230-260 K. Moreover, the transition temperature (TN) was found to decrease with increasing the size of A3+ ions. Zero field measurements indicated the formation of static antiferromagnetic (AF) order in ACu3Cr4O12 below TN. Furthermore, since the internal magnetic field in the AF phase is independent of A, the role of 4f electrons on the AF state is very limited and/or eventually absence in ACu3Cr4O12.

  11. A kinetic study of ferrocenium cation decomposition utilizing an integrated electrochemical methodology composed of cyclic voltammetry and amperometry.

    PubMed

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

    2014-11-21

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

  12. Octahedral cation partitioning in Mg,Fe2+-olivine. Mössbauer spectroscopic study of synthetic (Mg0.5 Fe2+ 0.5)2SiO4 (Fa50)

    NASA Astrophysics Data System (ADS)

    Morozov, Mikhail; Brinkmann, Christian; Grodzicki, Michael; Lottermoser, Werner; Tippelt, Gerold; Amthauer, Georg; Kroll, Herbert

    2005-11-01

    The high-temperature partitioning of Fe2+ and Mg between the two non-equivalent octahedral M1 and M2 sites in synthetic olivine (Fa50) was studied by Mössbauer spectroscopy. Powder samples have been equilibrated in annealing experiments performed under reducing oxygen fugacity at temperatures between 500 and 800°C followed by rapid quenching in order to prevent redistribution of cations. M-site ordering with Fe2+ preferring M1, Mg preferring M2 sites increases continuously with rising equilibrium temperature. K D values increase from 1.21 at 500°C to 1.48 at 750°C. The results are consistent with both room temperature as well as in situ high temperature single crystal X-ray diffraction experiments of Heinemann et al. [8, 9].

  13. Cation-exchanged SAPO-34 for adsorption-based hydrocarbon separations: predictions from dispersion-corrected DFT calculations.

    PubMed

    Fischer, Michael; Bell, Robert G

    2014-10-21

    The influence of the nature of the cation on the interaction of the silicoaluminophosphate SAPO-34 with small hydrocarbons (ethane, ethylene, acetylene, propane, propylene) is investigated using periodic density-functional theory calculations including a semi-empirical dispersion correction (DFT-D). Initial calculations are used to evaluate which of the guest-accessible cation sites in the chabazite-type structure is energetically preferred for a set of ten cations, which comprises four alkali metals (Li(+), Na(+), K(+), Rb(+)), three alkaline earth metals (Mg(2+), Ca(2+), Sr(2+)), and three transition metals (Cu(+), Ag(+), Fe(2+)). All eight cations that are likely to be found at the SII site (centre of a six-ring) are then included in the following investigation, which studies the interaction with the hydrocarbon guest molecules. In addition to the interaction energies, some trends and peculiarities regarding the adsorption geometries are analysed, and electron density difference plots obtained from the calculations are used to gain insights into the dominant interaction types. In addition to dispersion interactions, electrostatic and polarisation effects dominate for the main group cations, whereas significant orbital interactions are observed for unsaturated hydrocarbons interacting with transition metal (TM) cations. The differences between the interaction energies obtained for pairs of hydrocarbons of interest (such as ethylene-ethane and propylene-propane) deliver some qualitative insights: if this energy difference is large, it can be expected that the material will exhibit a high selectivity in the adsorption-based separation of alkene-alkane mixtures, which constitutes a problem of considerable industrial relevance. While the calculations show that TM-exchanged SAPO-34 materials are likely to exhibit a very high preference for alkenes over alkanes, the strong interaction may render an application in industrial processes impractical due to the large amount

  14. Development of a novel device to trap heavy metal cations: application of the specific interaction between heavy metal cation and mismatch DNA base pair.

    PubMed

    Torigoe, Hidetaka; Miyakawa, Yukako; Fukushi, Miyako; Ono, Akira; Kozasa, Tetsuo

    2009-01-01

    We have already found that Hg(II) cation specifically binds to T:T mismatch base pair in heteroduplex DNA, which increases the melting temperature of heteroduplex DNA involving T:T mismatch base pair by about 4 degrees C. We have also found that Ag(I) cation specifically binds to C:C mismatch base pair in heteroduplex DNA, which increases the melting temperature of heteroduplex DNA involving C:C mismatch base pair by about 4 degrees C. Using the specific interaction, we developed a novel device to trap each of Hg(II) and Ag(I) cation. The device is composed of 5'-biotinylated T-rich or C-rich DNA oligonucleotides, BIO-T20: 5'-Bio-T(20)-3' or BIO-C20: 5'-Bio-C(20)-3' (Bio is a biotin), immobilized on streptavidin-coated polystylene beads. When the BIO-T20-immobilized beads were added to a solution containing Hg(II) cation, and the beads trapping Hg(II) cation were collected by centrifugation, almost all of Hg(II) cation were removed from the solution. Also, when the BIO-C20-immobilized beads were added to a solution containing Ag(I) cation, and the beads trapping Ag(I) cation were collected by centrifugation, almost all of Ag(I) cation were removed from the solution. We conclude that, using the novel device developed in this study, Hg(II) and Ag(I) cation can be effectively removed from the solution.

  15. DOTAP cationic liposomes prefer relaxed over supercoiled plasmids.

    PubMed

    Even-Chen, S; Barenholz, Y

    2000-12-20

    Cationic liposomes and DNA interact electrostatically to form complexes called lipoplexes. The amounts of unbound (free) DNA in a mixture of cationic liposomes and DNA at different cationic lipid:DNA molar ratios can be used to describe DNA binding isotherms; these provide a measure of the binding efficiency of DNA to different cationic lipid formulations at various medium conditions. In order to quantify the ratio between the various forms of naked DNA and supercoiled, relaxed and single-stranded DNA, and the ratio between cationic lipid bound and unbound DNA of various forms we developed a simple, sensitive quantitative assay using agarose gel electrophoresis, followed by staining with the fluorescent cyanine DNA dyes SYBR Green I or SYBR Gold. This assay was compared with that based on the use of ethidium bromide (the most commonly used nucleic acid stain). Unlike ethidium bromide, SYBR Green I DNA sensitivity and concentration-dependent fluorescence intensity were identical for supercoiled and nicked-relaxed forms. DNA detection by SYBR Green I in solution is approximately 40-fold more sensitive than by ethidium bromide for double-stranded DNA and approximately 10-fold for single-stranded DNA, and in agarose gel it is 16-fold more sensitive for double-stranded DNA compared with ethidium bromide. SYBR Gold performs similarly to SYBR Green I. This study shows that: (a) there is no significant difference in DNA binding isotherms to the monocationic DOTAP (DOTAP/DOPE) liposomes and to the polycationic DOSPA (DOSPA/DOPE) liposomes, even when four DOSPA positive charges are involved in the electrostatic interaction with DNA; (b) the helper lipids affect DNA binding, as DOTAP/DOPE liposomes bind more DNA than DOTAP/cholesterol; (c) in the process of lipoplex formation, when the DNA is a mixture of two forms, supercoiled and nicked-relaxed (open circular), there is a preference for the binding to the cationic liposomes of plasmid DNA in the nicked-relaxed over the

  16. Infrared Spectroscopy of the Mass 31 Cation: Protonated Formaldehyde VS. The Triplet Methoxy Cation

    NASA Astrophysics Data System (ADS)

    Mosley, J. D.; Cheng, T. C.; Duncan, M. A.

    2012-06-01

    The m/z=31 cation is produced by ionization and fragmentation of methanol, ethanol, dimethyl ether, etc. Two structures have been proposed, protonated formaldehyde (^1CH_2OH^+) and the triplet methoxy cation (^3CH_3O^+). The infrared spectrum of the mass 31 cation is obtained using infrared photodissociation spectroscopy with Ar tagging. The spectrum reveals the presence of two stable isomers, protonated formaldehyde (^1CH_2OH^+) and the triplet methoxy cation (^3CH_3O^+). The triplet methoxy cation has been studied extensively and is predicted to interconvert to protonated formaldehyde through an essentially barrierless process on a timescale much faster than our experiment (>100 μs). The presence of two structural isomers is verified by comparison of spectra from different precursors and spectra of different temperature ions from the same precursor.

  17. Cation distribution in NiZn-ferrite films determined using x-ray absorption fine structure

    NASA Astrophysics Data System (ADS)

    Harris, V. G.; Koon, N. C.; Williams, C. M.; Zhang, Q.; Abe, M.

    1996-04-01

    We have applied extended x-ray absorption fine structure (EXAFS) spectroscopy to study the cation distribution in a series of spin-sprayed NiZn-ferrite films, Ni0.15ZnyFe2.85-yO4 (y=0.16, 0.23, 0.40, 0.60). The Ni, Zn, and Fe EXAFS were collected from each sample and analyzed to Fourier transforms. Samples of Ni-ferrite, Zn-ferrite, and magnetite were similarly studied as empirical standards. These standards, together with EXAFS data generated from the theoretical EXAFS FEFF codes, allowed the correlation of features in the Fourier transforms with specific lattice sites in the spinel unit cell. We find that the Ni ions reside mostly on the octahedral (B) sites whereas the Zn ions are predominantly on the tetrahedral (A) sites. The Fe ions reside on both A and B sites in a ratio determined by the ratio of Zn/Fe. The addition of Zn displaces a larger fraction of Fe cations onto the B sites serving to increase the net magnetization. The fraction of A site Ni ions is measured to increase peaking at ≊25% for y=0.6. At higher Zn concentrations (y≥0.5) the lattice experiences local distortions around the Zn sites causing a decrease in the superexchange resulting in a decrease in the net magnetization.

  18. Tannin-immobilized cellulose hydrogel fabricated by a homogeneous reaction as a potential adsorbent for removing cationic organic dye from aqueous solution.

    PubMed

    Pei, Ying; Chu, Shan; Chen, Yue; Li, Zhidong; Zhao, Jin; Liu, Shuqi; Wu, Xingjun; Liu, Jie; Zheng, Xuejing; Tang, Keyong

    2017-10-01

    Tannin-immobilized cellulose (CT) hydrogels were successfully fabricated by homogeneous immobilization and crosslinking reaction via a simple method. The structures and properties of hydrogels were characterized by SEM and mechanical test. Methlyene Blue (MB) was selected as a cationic dye model, and the adsorption ability of CT hydrogel was evaluated. Tannins immobilized acted as adsorbent sites which combined MB by electrostatic attraction, resulting in the attractive adsorption ability of CT hydrogel. Adsorption kinetics could be better described by the pseudo-second-order model, and the absorption behaviors were in agreement with a Langmuir isotherm. The adsorption-desorption cycle of CT hydrogel was repeated six times without significant loss of adsorption capacity. In this work, both tannin immobilization and hydrogel formation were achieved simultaneously by a facile homogeneous reaction, providing a new pathway to fabricate tannin-immobilized materials for water treatment. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Chemistry of alkali cation exchanged faujasite and mesoporous NaX using alkyl halides and phosphates

    NASA Astrophysics Data System (ADS)

    Lee, Min-Hong

    The purpose of this work was to increase the reactivity of Faujasite X (NaX) zeolite toward the reactive decontamination of materials subject to nucleophilic attack by means of zeolite cation optimization and by means of the synthesis of mesoporous Faujasite X. Primary alkyl halides and trialkyl phosphates have been the test materials on which the cation-optimized and mesoporous zeolites have been tested. In the alkali cation optimization work, reactions of methyl iodide and 1-chloropropane with alkali metal cation exchanged Faujasite zeolite X were investigated at room temperature. The reactivity of the framework and the product formation were shown to depend on zeolite framework counter-cation. A quantitative study of zeolite product formation has been carried out, primarily using solid-state NMR spectroscopy. Large alkali cations showed preference toward substitution chemistry. In contrast, alkyl halide exposed LiX and NaX zeolites underwent both substitution and elimination. Subsequently introduced water molecules led to hydrolysis of framework species that was sensitive to framework counter-cation. The mesoporous NaX zeolites work undertakes to test whether an improvement in surface chemical reactivity can be achieved by introducing mesopores into the already reactive nucleophilic microporous NaX zeolite. Incorporation of the polydiallyl dimethyl ammonium chloride (PDADMAC) template and the formation of mesopores in Faujasite X zeolite (NaX) were successful and well-characterized. The mesopores are proposed to have occurred from incorporation of the cationic PDADMAC polymer into the zeolite by compensating zeolite framework charge. Subsequent sodium cation exchange of calcined mesoporous NaX was shown to restore the chemical reactivity characteristic of as-synthesized NaX. Trialkyl organophosphorous compounds underwent substitution reactions. The reactivity of both microporous and mesoporous Faujasite zeolite X and the product formation was shown to depend on

  20. The influence of various cations on the catalytic properties of clays. [polymerization of alanine adenylate

    NASA Technical Reports Server (NTRS)

    Paecht-Horowitz, M.

    1978-01-01

    The polymerization of alanine adenylate in the presence of the sodium form of various clays was studied, and hectorite was found to cause more polymerization than nontronite and montmorillonite (in that order) although the differences were not great. The effect on polymerization of presaturating montmorillonite with different cations was determined. Hectorite, with increased basicity of the interspatial planes, allows polymerization of lysine, which montmorillonite does not. The general trend is that, for the same amino acid, higher degrees of polymerization are obtained when the cation in the octahedral lattice of the clay is divalent rather than trivalent. With the exchangeable cations the order is reversed, for a reason that is explained. The main role of clays in the polymerization mechanism of amino acids is concentration and neutralization of charges.

  1. Acation-anion regulation” synergistic anode host for dendrite-free lithium metal batteries

    PubMed Central

    Zhang, Weidong; Zhuang, Houlong L.; Fan, Lei; Gao, Lina; Lu, Yingying

    2018-01-01

    Dendritic Li deposition has been “a Gordian knot” for almost half a century, which significantly hinders the practical use of high-energy lithium metal batteries (LMBs). The underlying mechanisms of this dendrite formation are related to the preferential lithium deposition on the tips of the protuberances of the anode surface and also associated with the concentration gradient or even depletion of anions during cycling. Therefore, a synergistic regulation of cations and anions at the interface is vital to promoting dendrite-free Li anodes. An ingenious molecular structure is designed to realize the “cation-anion regulation” with strong interactions between adsorption sites and ions at the molecular level. A quaternized polyethylene terephthalate interlayer with a “lithiophilic” ester building block and an “anionphilic” quaternary ammonium functional block can guide ions to form dendrite-free Li metal deposits at an ultrahigh current density of 10 mA cm−2, enabling stable LMBs. PMID:29507888

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

    PubMed Central

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

    1986-01-01

    The mechanism by which sickle cells and xerocytic red cells become depleted of cations in vivo has not been identified previously. Both types of cells exhibit elevated permeabilities to sodium and potassium, in the case of sickle cells, when deoxygenated. The ouabain-insensitive fluxes of sodium and potassium were equivalent, however, in both cell types under these conditions. When incubated 18 hours in vitro, sickle cells lost cations but only when deoxygenated. This cation depletion was blocked by ouabain, removal of external potassium, or pretreatment with 4,4'-diisothiocyanostilbene-2,2'-disulfonate, which blocks the increase in cation permeability induced by deoxygenation. The loss of cation exhibited by oxygenated xerocytes similarly incubated was also blocked by ouabain. These data support the hypothesis that the elevated "passive" cation fluxes of xerocytes and deoxygenated sickle cells are not directly responsible for cation depletion of these cells; rather, these pathologic leaks interact with the sodium pump to produce a net loss of cellular cation. PMID:2430999

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

    PubMed

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

    1986-12-01

    The mechanism by which sickle cells and xerocytic red cells become depleted of cations in vivo has not been identified previously. Both types of cells exhibit elevated permeabilities to sodium and potassium, in the case of sickle cells, when deoxygenated. The ouabain-insensitive fluxes of sodium and potassium were equivalent, however, in both cell types under these conditions. When incubated 18 hours in vitro, sickle cells lost cations but only when deoxygenated. This cation depletion was blocked by ouabain, removal of external potassium, or pretreatment with 4,4'-diisothiocyanostilbene-2,2'-disulfonate, which blocks the increase in cation permeability induced by deoxygenation. The loss of cation exhibited by oxygenated xerocytes similarly incubated was also blocked by ouabain. These data support the hypothesis that the elevated "passive" cation fluxes of xerocytes and deoxygenated sickle cells are not directly responsible for cation depletion of these cells; rather, these pathologic leaks interact with the sodium pump to produce a net loss of cellular cation.

  4. Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide

    DOE PAGES

    Resasco, Joaquin; Chen, Leanne D.; Clark, Ezra; ...

    2017-07-24

    The electrochemical reduction of CO 2 is known to be influenced by the identity of the alkali metal cation in the electrolyte; however, a satisfactory explanation for this phenomenon has not been developed. Here we present the results of experimental and theoretical studies aimed at elucidating the effects of electrolyte cation size on the intrinsic activity and selectivity of metal catalysts for the reduction of CO 2. Experiments were conducted under conditions where the influence of electrolyte polarization is minimal in order to show that cation size affects the intrinsic rates of formation of certain reaction products, most notably formore » HCOO –, C 2H 4, and C 2H 5OH over Cu(100)- and Cu(111)-oriented thin films, and for CO and HCOO– over polycrystalline Ag and Sn. Interpretation of the findings for CO 2 reduction was informed by studies of the reduction of glyoxal and CO, key intermediates along the reaction pathway to final products. Density functional theory calculations show that the alkali metal cations influence the distribution of products formed as a consequence of electrostatic interactions between solvated cations present at the outer Helmholtz plane and adsorbed species having large dipole moments. As a result, the observed trends in activity with cation size are attributed to an increase in the concentration of cations at the outer Helmholtz plane with increasing cation size.« less

  5. Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide

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

    Resasco, Joaquin; Chen, Leanne D.; Clark, Ezra

    The electrochemical reduction of CO 2 is known to be influenced by the identity of the alkali metal cation in the electrolyte; however, a satisfactory explanation for this phenomenon has not been developed. Here we present the results of experimental and theoretical studies aimed at elucidating the effects of electrolyte cation size on the intrinsic activity and selectivity of metal catalysts for the reduction of CO 2. Experiments were conducted under conditions where the influence of electrolyte polarization is minimal in order to show that cation size affects the intrinsic rates of formation of certain reaction products, most notably formore » HCOO –, C 2H 4, and C 2H 5OH over Cu(100)- and Cu(111)-oriented thin films, and for CO and HCOO– over polycrystalline Ag and Sn. Interpretation of the findings for CO 2 reduction was informed by studies of the reduction of glyoxal and CO, key intermediates along the reaction pathway to final products. Density functional theory calculations show that the alkali metal cations influence the distribution of products formed as a consequence of electrostatic interactions between solvated cations present at the outer Helmholtz plane and adsorbed species having large dipole moments. As a result, the observed trends in activity with cation size are attributed to an increase in the concentration of cations at the outer Helmholtz plane with increasing cation size.« less

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

    PubMed

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

    2017-05-01

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

  7. Effect of Siloxane Ring Strain and Cation Charge Density on the Formation of Coordinately Unsaturated Metal Sites on Silica: Insights from Density Functional Theory (DFT) Studies

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

    Das, Ujjal; Zhang, Guanghui; Hu, Bo

    2015-10-28

    Amorphous silica (SiO 2) is commonly used as a support in heterogeneous catalysis. However, due to the structural disorder and temperature induced change of surface morphology, the structures of silica supported metal catalysts are difficult to determine. Most studies are primarily focused on understanding the interactions of different types of surface hydroxyl groups with metal ions. In comparison, the effect of siloxane ring size on the structure of silica supported metal catalysts and how it affects catalytic activity is poorly understood. Here, we have used density functional theory calculations to understand the effect of siloxane ring strain on structure andmore » activity of different monomeric Lewis acid metal sites on silica. In particular, we have found that large siloxane rings favor strong dative bonding interaction between metal ion and surface hydroxyls, leading to the formation of high-coordinate metal sites. In comparison, metal-silanol interaction is weak in small siloxane rings, resulting in low-coordinate metal sites. The physical origin of this size dependence is associated with siloxane ring strain, and, a correlation between metal-silanol interaction energy and ring strain energy has been observed. In addition to ring strain, the strength of the metal-silanol interaction also depends on the positive charge density of the cations. In fact, a correlation also exists between metal-silanol interaction energy and charge density of several first-row transition and post-transition metals. The theoretical results are compared with the EXAFS data of monomeric Zn(II) and Ga(III) ions grafted on silica. In conclusion, the molecular level insights of how metal ion coordination on silica depends on siloxane ring strain and cation charge density will be useful in the synthesis of new catalysts.« less

  8. Long-term effects of commercial sawlog harvest on soil cation concentrations

    Treesearch

    Jennifer D. Knoepp; Wayne T. Swank

    1997-01-01

    There is increasing concern about the effects of nutrient removal associated with various forest harvesting practices on long-term site productivity. The authors measured exchangeable soil cation concentration responses to a commercial clearcut sawlog harvest in mixed hardwoods on a 59-ha watershed in the Southern Appalachians. Soils were sampled 17 months prior to and...

  9. p53 Mutagenesis by Benzo[a]pyrene derived Radical Cations

    PubMed Central

    Sen, Sushmita; Bhojnagarwala, Pratik; Francey, Lauren; Lu, Ding; Jeffrey Field, Trevor M. Penning

    2013-01-01

    Benzo[a]pyrene (B[a]P), a major human carcinogen in combustion products such as cigarette smoke and diesel exhaust, is metabolically activated into DNA-reactive metabolites via three different enzymatic pathways. The pathways are the anti-(+)-benzo[a]pyrene 7,8-diol 9, 10-epoxide pathway (P450/ epoxide hydrolase catalyzed) (B[a]PDE), the benzo[a]pyrene o-quinone pathway (aldo ketose reductase (AKR) catalyzed) and the B[a]P radical cation pathway (P450 peroxidase catalyzed). We used a yeast p53 mutagenesis system to assess mutagenesis by B[a]P radical cations. Because radical cations are short-lived, they were generated in situ by reacting B[a]P with cumene hydroperoxide (CuOOH) and horse radish peroxidase (HRP) and then monitoring the generation of the more stable downstream products, B[a]P-1,6-dione and B[a]P-3,6-dione. Based on the B[a]P-1,6 and 3,6-dione formation, approximately 4µM of radical cation was generated. In the mutagenesis assays, the radical cations produced in situ showed a dose-dependent increase in mutagenicity from 0.25 µM to 10 µM B[a]P with no significant increase seen with further escalation to 50 µM B[a]P. However, mutagenesis was 200-fold less than with the AKR pathway derived B[a]P, 7–8 dione. Mutant p53 plasmids, which yield red colonies, were recovered from the yeast to study the pattern and spectrum of mutations. The mutation pattern observed was G to T (31%) > G to C (29%) > G to A (14%). The frequency of codons mutated by the B[a]P radical cations was essentially random and not enriched at known cancer hotspots. The quinone products of radical cations, B[a]P-1,6-dione and B[a]P-3,6-dione were more mutagenic than the radical cation reactions, but still less mutagenic than AKR derived B[a]P-7,8-dione. We conclude that B[a]P radical cations and their quinone products are weakly mutagenic in this yeast-based system compared to redox cycling PAH o-quinones. PMID:22768918

  10. Molecular Dynamics Study of Crystalline Swelling of Montmorillonite as Affected by Interlayer Cation Hydration

    NASA Astrophysics Data System (ADS)

    Li, Hongliang; Song, Shaoxian; Dong, Xianshu; Min, Fanfei; Zhao, Yunliang; Peng, Chenliang; Nahmad, Yuri

    2018-04-01

    Swelling of montmorillonite (Mt) is an important factor for many industrial applications. In this study, crystalline swelling of alkali-metal- and alkaline-earth-metal-Mt has been studied through energy optimization and molecular dynamics simulations using the clay force field by Materials Studio 8.0. The delamination and exfoliation of Mt are primarily realized by crystalline swelling caused by the enhanced interlayer cation hydration. The initial position of the interlayer cations and water molecules is the dominated factor for the accuracy of the Mt simulations. Crystalline swelling can be carried out in alkali-metal-Mt and Mg-Mt but with difficulty in Ca-Mt, Sr-Mt and Ba-Mt. The crystalline swelling capacity values are in the order Na-Mt > K-Mt > Cs-Mt > Mg-Mt. This order of crystalline swelling of Mt in the same group can be attributed to the differences between the interlayer cation hydration strengths. In addition, the differences in the crystalline swelling between the alkali-metal-Mt and alkaline-earth-metal-Mt can be primarily attributed to the valence of the interlayer cations.

  11. Structural Basis for Xenon Inhibition in a Cationic Pentameric Ligand-Gated Ion Channel

    PubMed Central

    Sauguet, Ludovic; Fourati, Zeineb; Prangé, Thierry; Delarue, Marc; Colloc'h, Nathalie

    2016-01-01

    GLIC receptor is a bacterial pentameric ligand-gated ion channel whose action is inhibited by xenon. Xenon has been used in clinical practice as a potent gaseous anaesthetic for decades, but the molecular mechanism of interactions with its integral membrane receptor targets remains poorly understood. Here we characterize by X-ray crystallography the xenon-binding sites within both the open and “locally-closed” (inactive) conformations of GLIC. Major binding sites of xenon, which differ between the two conformations, were identified in three distinct regions that all belong to the trans-membrane domain of GLIC: 1) in an intra-subunit cavity, 2) at the interface between adjacent subunits, and 3) in the pore. The pore site is unique to the locally-closed form where the binding of xenon effectively seals the channel. A putative mechanism of the inhibition of GLIC by xenon is proposed, which might be extended to other pentameric cationic ligand-gated ion channels. PMID:26910105

  12. Structural Basis for Xenon Inhibition in a Cationic Pentameric Ligand-Gated Ion Channel.

    PubMed

    Sauguet, Ludovic; Fourati, Zeineb; Prangé, Thierry; Delarue, Marc; Colloc'h, Nathalie

    2016-01-01

    GLIC receptor is a bacterial pentameric ligand-gated ion channel whose action is inhibited by xenon. Xenon has been used in clinical practice as a potent gaseous anaesthetic for decades, but the molecular mechanism of interactions with its integral membrane receptor targets remains poorly understood. Here we characterize by X-ray crystallography the xenon-binding sites within both the open and "locally-closed" (inactive) conformations of GLIC. Major binding sites of xenon, which differ between the two conformations, were identified in three distinct regions that all belong to the trans-membrane domain of GLIC: 1) in an intra-subunit cavity, 2) at the interface between adjacent subunits, and 3) in the pore. The pore site is unique to the locally-closed form where the binding of xenon effectively seals the channel. A putative mechanism of the inhibition of GLIC by xenon is proposed, which might be extended to other pentameric cationic ligand-gated ion channels.

  13. IR signature of the photoionization-induced hydrophobic-->hydrophilic site switching in phenol-Arn clusters

    NASA Astrophysics Data System (ADS)

    Ishiuchi, Shun-ichi; Sakai, Makoto; Tsuchida, Yuji; Takeda, Akihiro; Kawashima, Yasutake; Dopfer, Otto; Müller-Dethlefs, Klaus; Fujii, Masaaki

    2007-09-01

    IR spectra of phenol-Arn (PhOH-Arn) clusters with n =1 and 2 were measured in the neutral and cationic electronic ground states in order to determine the preferential intermolecular ligand binding motifs, hydrogen bonding (hydrophilic interaction) versus π bonding (hydrophobic interaction). Analysis of the vibrational frequencies of the OH stretching motion, νOH, observed in nanosecond IR spectra demonstrates that neutral PhOH-Ar and PhOH -Ar2 as well as cationic PhOH +-Ar have a π-bound structure, in which the Ar atoms bind to the aromatic ring. In contrast, the PhOH +-Ar2 cluster cation is concluded to have a H-bound structure, in which one Ar atom is hydrogen-bonded to the OH group. This π →H binding site switching induced by ionization was directly monitored in real time by picosecond time-resolved IR spectroscopy. The π-bound νOH band is observed just after the ionization and disappears simultaneously with the appearance of the H-bound νOH band. The analysis of the picosecond IR spectra demonstrates that (i) the π →H site switching is an elementary reaction with a time constant of ˜7ps, which is roughly independent of the available internal vibrational energy, (ii) the barrier for the isomerization reaction is rather low(<100cm-1), (iii) both the position and the width of the H-bound νOH band change with the delay time, and the time evolution of these spectral changes can be rationalized by intracluster vibrational energy redistribution occurring after the site switching. The observation of the ionization-induced switch from π bonding to H bonding in the PhOH +-Ar2 cation corresponds to the first manifestation of an intermolecular isomerization reaction in a charged aggregate.

  14. Comparison of multilayer formation between different cellulose nanofibrils and cationic polymers.

    PubMed

    Eronen, Paula; Laine, Janne; Ruokolainen, Janne; Osterberg, Monika

    2012-05-01

    The multilayer formation between polyelectrolytes of opposite charge offers possibility for creating new tailored materials. Exchanging one or both components for charged nanofibrillated cellulose (NFC) further increases the variety of achievable properties. We explored this by introducing unmodified, low charged NFC and high charged TEMPO-oxidized NFC. Systematic evaluation of the effect of both NFC charge and properties of cationic polyelectrolytes on the structure of the multilayers was performed. As the cationic component cationic NFC was compared with two different cationic polyelectrolytes, poly(dimethyldiallylammoniumchloride) and cationic starch. Quartz crystal microbalance with dissipation (QCM-D) was used to monitor the multilayer formation and AFM colloidal probe microscopy (CPM) was further applied to probe surface interactions in order to gain information about fundamental interactions and layer properties. Generally, the results verified the characteristic multilayer formation between NFC of different charge and how the properties of formed multilayers can be tuned. However, the strong nonelectrostatic affinity between cellulosic fibrils was observed. CPM measurements revealed monotonically repulsive forces, which were in good correspondence with the QCM-D observations. Significant increase in adhesive forces was detected between the swollen high charged NFC. Copyright © 2011 Elsevier Inc. All rights reserved.

  15. How Native and Alien Metal Cations Bind ATP: Implications for Lithium as a Therapeutic Agent

    NASA Astrophysics Data System (ADS)

    Dudev, Todor; Grauffel, Cédric; Lim, Carmay

    2017-02-01

    Adenosine triphosphate (ATP), the major energy currency of the cell, exists in solution mostly as ATP-Mg. Recent experiments suggest that Mg2+ interacts with the highly charged ATP triphosphate group and Li+ can co-bind with the native Mg2+ to form ATP-Mg-Li and modulate the neuronal purine receptor response. However, it is unclear how the negatively charged ATP triphosphate group binds Mg2+ and Li+ (i.e. which phosphate group(s) bind Mg2+/Li+) and how the ATP solution conformation depends on the type of metal cation and the metal-binding mode. Here, we reveal the preferred ATP-binding mode of Mg2+/Li+ alone and combined: Mg2+ prefers to bind ATP tridentately to each of the three phosphate groups, but Li+ prefers to bind bidentately to the terminal two phosphates. We show that the solution ATP conformation depends on the cation and its binding site/mode, but it does not change significantly when Li+ binds to Mg2+-loaded ATP. Hence, ATP-Mg-Li, like Mg2+-ATP, can fit in the ATP-binding site of the host enzyme/receptor, activating specific signaling pathways.

  16. Competition and enhancement effect in coremoval of atenolol and copper by an easily regenerative magnetic cation exchange resin.

    PubMed

    Li, Qimeng; Wang, Zheng; Li, Qiang; Shuang, Chendong; Zhou, Qing; Li, Aimin; Gao, Canzhu

    2017-07-01

    This paper aimed to investigate the removal of combined Cu 2+ and atenolol (ATL) in aqueous solution by using a newly synthesized magnetic cation exchange resin (MCER) as the adsorbent. The MCER exhibited efficient removal performance in sole, binary, pre-loading and saline systems. The adsorption kinetics of Cu 2+ and ATL fitted both pseudo-first-order and pseudo-second order model, while better described by pseudo-second order model in binary system. In mixed Cu 2+ and ATL solution, the adsorption of ATL was suppressed due to direct competition of carboxylic groups, while Cu 2+ adsorption was enhanced because of the formation of surface complexes. This increasing in heterogeneity was demonstrated by adsorption isotherms, which were more suitable for Freundlich model in binary system, while better described by Langmuir model in sole system. As proved by FTIR and XPS spectra, both amino and hydroxyl groups of ATL could form complexes with Cu 2+ . Decomplexing-bridging interaction was elucidated as the leading mechanism in coremoval of Cu 2+ and ATL, which involved [Cu-ATL] decomplexing and newly created Cu- or ATL sites for additional bridging. For saline system, the resulting competition and enhancement effects in mixed solution were amplified with the addition of co-existing cations. Moreover, the MCER could be effectively regenerated by 0.01 M HCl solution and maintain high stability over 5 adsorption-desorption cycles, which render it great potential for practical applications. Copyright © 2017. Published by Elsevier Ltd.

  17. Charge states of ions, and mechanisms of charge ordering transitions

    NASA Astrophysics Data System (ADS)

    Pickett, Warren E.; Quan, Yundi; Pardo, Victor

    2014-07-01

    To gain insight into the mechanism of charge ordering transitions, which conventionally are pictured as a disproportionation of an ion M as 2Mn+→M(n+1)+ + M(n-1)+, we (1) review and reconsider the charge state (or oxidation number) picture itself, (2) introduce new results for the putative charge ordering compound AgNiO2 and the dual charge state insulator AgO, and (3) analyze the cationic occupations of the actual (not formal) charge, and work to reconcile the conundrums that arise. We establish that several of the clearest cases of charge ordering transitions involve no disproportion (no charge transfer between the cations, and hence no charge ordering), and that the experimental data used to support charge ordering can be accounted for within density functional-based calculations that contain no charge transfer between cations. We propose that the charge state picture retains meaning and importance, at least in many cases, if one focuses on Wannier functions rather than atomic orbitals. The challenge of modeling charge ordering transitions with model Hamiltonians isdiscussed.

  18. Chemical ordering in substituted fluorite oxides: a computational investigation of Ho 2Zr 2O 7 and RE 2Th 2O 7 (RE=Ho, Y, Gd, Nd, La)

    DOE PAGES

    Solomon, Jonathan M.; Shamblin, Jacob; Lang, Maik; ...

    2016-12-12

    Fluorite-structured oxides find widespread use for applications spanning nuclear energy and waste containment, energy conversion, and sensing. In such applications the host tetravalent cation is often partially substituted by trivalent cations, with an associated formation of charge-compensating oxygen vacancies. The stability and properties of such materials are known to be influenced strongly by chemical ordering of the cations and vacancies, and the nature of such ordering and associated energetics are thus of considerable interest. Here we employ density-functional theory (DFT) calculations to study the structure and energetics of cation and oxygen-vacancy ordering in Ho 2Zr 2O 7. In a recentmore » neutron total scattering study, solid solutions in this system were reported to feature local chemical ordering based on the fluorite-derivative weberite structure. The calculations show a preferred chemical ordering qualitatively consistent with these findings, and yield values for the ordering energy of 9.5 kJ/mol-cation. Similar DFT calculations are applied to additional RE 2Th 2O 7'' fluorite compounds, spanning a range of values for the ratio of the tetravalent and trivalent (RE) cation radii. Finally, the results demonstrate that weberite-type order becomes destabilized with increasing values of this size ratio, consistent with an increasing energetic preference for the tetravalent cations to have higher oxygen coordination.« less

  19. Chemical ordering in substituted fluorite oxides: a computational investigation of Ho2Zr2O7 and RE2Th2O7 (RE=Ho, Y, Gd, Nd, La).

    PubMed

    Solomon, Jonathan M; Shamblin, Jacob; Lang, Maik; Navrotsky, Alexandra; Asta, Mark

    2016-12-12

    Fluorite-structured oxides find widespread use for applications spanning nuclear energy and waste containment, energy conversion, and sensing. In such applications the host tetravalent cation is often partially substituted by trivalent cations, with an associated formation of charge-compensating oxygen vacancies. The stability and properties of such materials are known to be influenced strongly by chemical ordering of the cations and vacancies, and the nature of such ordering and associated energetics are thus of considerable interest. Here we employ density-functional theory (DFT) calculations to study the structure and energetics of cation and oxygen-vacancy ordering in Ho 2 Zr 2 O 7 . In a recent neutron total scattering study, solid solutions in this system were reported to feature local chemical ordering based on the fluorite-derivative weberite structure. The calculations show a preferred chemical ordering qualitatively consistent with these findings, and yield values for the ordering energy of 9.5 kJ/mol-cation. Similar DFT calculations are applied to additional RE 2 Th 2 O 7 fluorite compounds, spanning a range of values for the ratio of the tetravalent and trivalent (RE) cation radii. The results demonstrate that weberite-type order becomes destabilized with increasing values of this size ratio, consistent with an increasing energetic preference for the tetravalent cations to have higher oxygen coordination.

  20. Chemical ordering in substituted fluorite oxides: a computational investigation of Ho2Zr2O7 and RE2Th2O7 (RE=Ho, Y, Gd, Nd, La)

    PubMed Central

    Solomon, Jonathan M.; Shamblin, Jacob; Lang, Maik; Navrotsky, Alexandra; Asta, Mark

    2016-01-01

    Fluorite-structured oxides find widespread use for applications spanning nuclear energy and waste containment, energy conversion, and sensing. In such applications the host tetravalent cation is often partially substituted by trivalent cations, with an associated formation of charge-compensating oxygen vacancies. The stability and properties of such materials are known to be influenced strongly by chemical ordering of the cations and vacancies, and the nature of such ordering and associated energetics are thus of considerable interest. Here we employ density-functional theory (DFT) calculations to study the structure and energetics of cation and oxygen-vacancy ordering in Ho2Zr2O7. In a recent neutron total scattering study, solid solutions in this system were reported to feature local chemical ordering based on the fluorite-derivative weberite structure. The calculations show a preferred chemical ordering qualitatively consistent with these findings, and yield values for the ordering energy of 9.5 kJ/mol-cation. Similar DFT calculations are applied to additional RE2Th2O7 fluorite compounds, spanning a range of values for the ratio of the tetravalent and trivalent (RE) cation radii. The results demonstrate that weberite-type order becomes destabilized with increasing values of this size ratio, consistent with an increasing energetic preference for the tetravalent cations to have higher oxygen coordination. PMID:27941870

  1. Chemical ordering in substituted fluorite oxides: a computational investigation of Ho2Zr2O7 and RE2Th2O7 (RE=Ho, Y, Gd, Nd, La)

    NASA Astrophysics Data System (ADS)

    Solomon, Jonathan M.; Shamblin, Jacob; Lang, Maik; Navrotsky, Alexandra; Asta, Mark

    2016-12-01

    Fluorite-structured oxides find widespread use for applications spanning nuclear energy and waste containment, energy conversion, and sensing. In such applications the host tetravalent cation is often partially substituted by trivalent cations, with an associated formation of charge-compensating oxygen vacancies. The stability and properties of such materials are known to be influenced strongly by chemical ordering of the cations and vacancies, and the nature of such ordering and associated energetics are thus of considerable interest. Here we employ density-functional theory (DFT) calculations to study the structure and energetics of cation and oxygen-vacancy ordering in Ho2Zr2O7. In a recent neutron total scattering study, solid solutions in this system were reported to feature local chemical ordering based on the fluorite-derivative weberite structure. The calculations show a preferred chemical ordering qualitatively consistent with these findings, and yield values for the ordering energy of 9.5 kJ/mol-cation. Similar DFT calculations are applied to additional RE2Th2O7 fluorite compounds, spanning a range of values for the ratio of the tetravalent and trivalent (RE) cation radii. The results demonstrate that weberite-type order becomes destabilized with increasing values of this size ratio, consistent with an increasing energetic preference for the tetravalent cations to have higher oxygen coordination.

  2. Selection Rule of Preferred Doping Site for n-Type Oxides

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

    Li, C.; Li, J.; Li, S. S.

    2012-06-25

    Using first-principles calculations and analysis, we show that to create shallow n-type dopants in oxides, anion site doping is preferred for more covalent oxides such as SnO{sub 2} and cation site doping is preferred for more ionic oxides such as ZnO. This is because for more ionic oxides, the conduction band minimum (CBM) state actually contains a considerable amount of O 3s orbitals, thus anion site doping can cause large perturbation on the CBM and consequently produces deeper donor levels. We also show that whether it is cation site doping or anion site doping, the oxygen-poor condition should always bemore » used.« less

  3. Absorption and electroabsorption spectra of carotenoid cation radical and dication

    NASA Astrophysics Data System (ADS)

    Krawczyk, Stanisław

    1998-05-01

    Radical cations and dications of two carotenoids astaxanthin and canthaxanthin were prepared by oxidation with FeCl 3 in fluorinated alcohols at room temperature. Absorption and electroabsorption (Stark effect) spectra were recorded for astaxanthin cations in mixed frozen matrices at temperatures about 160 K. The D 0→D 2 transition in cation radical is at 835 nm. The electroabsorption spectrum for the D 0→D 2 transition exhibits a negative change of molecular polarizability, Δ α=-1.2·10 -38 C·m 2/V (-105 A 3), which seems to originate from the change in bond order alternation in the ground state rather than from the electric field-induced interaction of D 1 and D 2 excited states. Absorption spectrum of astaxanthin dication is located at 715-717 nm, between those of D 0→D 2 in cation radical and S 0→S 2 in neutral carotenoid. Its shape reflects a short vibronic progression and strong inhomogeneous broadening. The polarizability change on electronic excitation, Δ α=2.89·10 -38 C·m 2/V (260 A 3), is five times smaller than in neutral astaxanthin. This value reflects the larger energetic distance from the lowest excited state to the higher excited states than in the neutral molecule.

  4. Postsynthetic Doping of MnCl2 Molecules into Preformed CsPbBr3 Perovskite Nanocrystals via a Halide Exchange-Driven Cation Exchange.

    PubMed

    Huang, Guangguang; Wang, Chunlei; Xu, Shuhong; Zong, Shenfei; Lu, Ju; Wang, Zhuyuan; Lu, Changgui; Cui, Yiping

    2017-08-01

    Unlike widely used postsynthetic halide exchange for CsPbX 3 (X is halide) perovskite nanocrystals (NCs), cation exchange of Pb is of a great challenge due to the rigid nature of the Pb cationic sublattice. Actually, cation exchange has more potential for rendering NCs with peculiar properties. Herein, a novel halide exchange-driven cation exchange (HEDCE) strategy is developed to prepare dually emitting Mn-doped CsPb(Cl/Br) 3 NCs via postsynthetic replacement of partial Pb in preformed perovskite NCs. The basic idea for HEDCE is that the partial cation exchange of Pb by Mn has a large probability to occur as a concomitant result for opening the rigid halide octahedron structure around Pb during halide exchange. Compared to traditional ionic exchange, HEDCE is featured by proceeding of halide exchange and cation exchange at the same time and lattice site. The time and space requirements make only MnCl 2 molecules (rather than mixture of Mn and Cl ions) capable of doping into perovskite NCs. This special molecular doping nature results in a series of unusual phenomenon, including long reaction time, core-shell structured mid states with triple emission bands, and dopant molecules composition-dependent doping process. As-prepared dual-emitting Mn-doped CsPb(Cl/Br) 3 NCs are available for ratiometric temperature sensing. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Revisiting caffeate's capabilities as a complexation agent to silver cation in mining processes by means of the dual descriptor--a conceptual DFT approach.

    PubMed

    Martínez-Araya, Jorge Ignacio

    2012-09-01

    Caffeic acid (C(9)H(8)O(4)) and its conjugate base C(9)H(7)O(4) (-) (anionic form-known as caffeate) were analyzed computationally through the use of quantum chemistry to assess their intrinsic global and local reactivity using the tools of conceptual density functional theory. The anionic form was found to be better at coordinating the silver cation than caffeic acid thus suggesting the use of caffeate as a complexation agent. The complexation capability of caffeate was compared with that of some of the most common ligand agents used to coordinate silver cations. Local reactivity descriptors allowed identification of the preferred sites on caffeate for silver cation coordination thus generating a plausible silver complex. All silver complexes were analyzed thermodynamically considering interaction energies in both gas and aqueous phases; the complexation free energy in aqueous phase was also determined. These results suggest that more attention be paid to the caffeate anion and its derivatives because this work has shed new light on the behavior of this anion in the recovery of silver cations that could be exploited in silver mining processes in a environmentally friendly way.

  6. Orbital ordering in FeV2O4: Spinel with two orbitally active sites

    NASA Astrophysics Data System (ADS)

    Sarkar, Soumyajit; Saha-Dasgupta, T.

    2011-12-01

    By employing first-principles electronic structure calculations, we investigate orbital ordering in FeV2O4, a spinel with orbital degrees of freedom both at Fe and V sites that exhibits two tetragonal phases, one compressed at high temperature and another elongated at low temperature. Our first-principles study shows the ferro-orbital ordering of dx2-y2 and d3z2-r2 types at Fe sites at the high- and low-temperature phases, respectively. The orbital ordering at V sites is found to consist of orbital chains running along different directions with orbitals rotated alternatively within each chain, similar to that found for MnV2O4 [S. Sarkar , Phys. Rev. Lett.PRLTAO0031-900710.1103/PhysRevLett.102.216405 102, 216405 (2009)]. Further, we find that the single-ion anisotropy effect with hard and easy c axis favors the compressed and elongated tetrahedral shapes. This gives rise to magnetocrystalline anisotropy-dependent shapes, similar to that reported in the context of rare-earth-based magnetic shape memory alloys.

  7. A calix[4]arene strapped calix[4]pyrrole: an ion-pair receptor displaying three different cesium cation recognition modes.

    PubMed

    Kim, Sung Kuk; Sessler, Jonathan L; Gross, Dustin E; Lee, Chang-Hee; Kim, Jong Seung; Lynch, Vincent M; Delmau, Laetitia H; Hay, Benjamin P

    2010-04-28

    An ion-pair receptor, the calix[4]pyrrole-calix[4]arene pseudodimer 2, bearing a strong anion-recognition site but not a weak cation-recognition site, has been synthesized and characterized by standard spectroscopic means and via single-crystal X-ray diffraction analysis. In 10% CD(3)OD in CDCl(3) (v/v), this new receptor binds neither the Cs(+) cation nor the F(-) anion when exposed to these species in the presence of other counterions; however, it forms a stable 1:1 solvent-separated CsF complex when exposed to these two ions in concert with one another in this same solvent mixture. In contrast to what is seen in the case of a previously reported crown ether "strapped" calixarene-calixpyrrole ion-pair receptor 1 (J. Am. Chem. Soc. 2008, 130, 13162-13166), where Cs(+) cation recognition takes place within the crown, in 2.CsF cation recognition takes place within the receptor cavity itself, as inferred from both single-crystal X-ray diffraction analyses and (1)H NMR spectroscopic studies. This binding mode is supported by calculations carried out using the MMFF94 force field model. In 10% CD(3)OD in CDCl(3) (v/v), receptor 2 shows selectivity for CsF over the Cs(+) salts of Cl(-), Br(-), and NO(3)(-) but will bind these other cesium salts in the absence of fluoride, both in solution and in the solid state. In the case of CsCl, an unprecedented 2:2 complex is observed in the solid state that is characterized by two different ion-pair binding modes. One of these consists of a contact ion pair with the cesium cation and chloride anion both being bound within the central binding pocket and in direct contact with one another. The other mode involves a chloride anion bound to the pyrrole NH protons of a calixpyrrole subunit and a cesium cation sandwiched between two cone shaped calix[4]pyrroles originating from separate receptor units. In contrast to what is seen for CsF and CsCl, single-crystal X-ray structural analyses and (1)H NMR spectroscopic studies reveal that

  8. Sn Cation Valency Dependence in Cation Exchange Reactions Involving Cu2-xSe Nanocrystals

    PubMed Central

    2014-01-01

    We studied cation exchange reactions in colloidal Cu2-xSe nanocrystals (NCs) involving the replacement of Cu+ cations with either Sn2+ or Sn4+ cations. This is a model system in several aspects: first, the +2 and +4 oxidation states for tin are relatively stable; in addition, the phase of the Cu2-xSe NCs remains cubic regardless of the degree of copper deficiency (that is, “x”) in the NC lattice. Also, Sn4+ ions are comparable in size to the Cu+ ions, while Sn2+ ones are much larger. We show here that the valency of the entering Sn ions dictates the structure and composition not only of the final products but also of the intermediate steps of the exchange. When Sn4+ cations are used, alloyed Cu2–4ySnySe NCs (with y ≤ 0.33) are formed as intermediates, with almost no distortion of the anion framework, apart from a small contraction. In this exchange reaction the final stoichiometry of the NCs cannot go beyond Cu0.66Sn0.33Se (that is Cu2SnSe3), as any further replacement of Cu+ cations with Sn4+ cations would require a drastic reorganization of the anion framework, which is not possible at the reaction conditions of the experiments. When instead Sn2+ cations are employed, SnSe NCs are formed, mostly in the orthorhombic phase, with significant, albeit not drastic, distortion of the anion framework. Intermediate steps in this exchange reaction are represented by Janus-type Cu2-xSe/SnSe heterostructures, with no Cu–Sn–Se alloys. PMID:25340627

  9. Block by Extracellular Divalent Cations of Drosophila Big Brain Channels Expressed in Xenopus Oocytes

    PubMed Central

    Yanochko, Gina M.; Yool, Andrea J.

    2004-01-01

    Drosophila Big Brain (BIB) is a transmembrane protein encoded by the neurogenic gene big brain (bib), which is important for early development of the fly nervous system. BIB expressed in Xenopus oocytes is a monovalent cation channel modulated by tyrosine kinase signaling. Results here demonstrate that the BIB conductance shows voltage- and dose-dependent block by extracellular divalent cations Ca2+ and Ba2+ but not by Mg2+ in wild-type channels. Site-directed mutagenesis of negatively charged glutamate (Glu274) and aspartate (Asp253) residues had no effect on divalent cation block. However, mutation of a conserved glutamate at position 71 (Glu71) in the first transmembrane domain (M1) altered channel properties. Mutation of Glu71 to Asp introduced a new sensitivity to block by extracellular Mg2+; substitutions with asparagine or glutamine decreased whole-cell conductance; and substitution with lysine compromised plasma membrane expression. Block by divalent cations is important in other ion channels for voltage-dependent function, enhanced signal resolution, and feedback regulation. Our data show that the wild-type BIB conductance is attenuated by external Ca2+, suggesting that endogenous divalent cation block might be relevant for enhancing signal resolution or voltage dependence for the native signaling process in neuronal cell fate determination. PMID:14990474

  10. Cationic electrodepositable coating composition comprising lignin

    DOEpatents

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

    2013-07-30

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

  11. Cation specific binding with protein surface charges

    PubMed Central

    Hess, Berk; van der Vegt, Nico F. A.

    2009-01-01

    Biological organization depends on a sensitive balance of noncovalent interactions, in particular also those involving interactions between ions. Ion-pairing is qualitatively described by the law of “matching water affinities.” This law predicts that cations and anions (with equal valence) form stable contact ion pairs if their sizes match. We show that this simple physical model fails to describe the interaction of cations with (molecular) anions of weak carboxylic acids, which are present on the surfaces of many intra- and extracellular proteins. We performed molecular simulations with quantitatively accurate models and observed that the order K+ < Na+ < Li+ of increasing binding affinity with carboxylate ions is caused by a stronger preference for forming weak solvent-shared ion pairs. The relative insignificance of contact pair interactions with protein surfaces indicates that thermodynamic stability and interactions between proteins in alkali salt solutions is governed by interactions mediated through hydration water molecules. PMID:19666545

  12. Cationic liposomes as vaccine adjuvants.

    PubMed

    Christensen, Dennis; Korsholm, Karen S; Rosenkrands, Ida; Lindenstrøm, Thomas; Andersen, Peter; Agger, Else Marie

    2007-10-01

    Cationic liposomes are lipid-bilayer vesicles with a positive surface charge that have re-emerged as a promising new adjuvant technology. Although there is some evidence that cationic liposomes themselves can improve the immune response against coadministered vaccine antigens, their main functions are to protect the antigens from clearance in the body and deliver the antigens to professional antigen-presenting cells. In addition, cationic liposomes can be used to introduce immunomodulators to enhance and modulate the immune response in a desirable direction and, thereby, represent an efficient tool when designing tailor-made adjuvants for specific disease targets. In this article we review the recent progress on cationic liposomes as vehicles, enhancing the effect of immunomodulators and the presentation of vaccine antigens.

  13. High-capacity cation-exchange column for enhanced resolution of adjacent peaks of cations in ion chromatography.

    PubMed

    Rey, M A

    2001-06-22

    One of the advantages of ion chromatography [Anal Chem. 47 (1975) 1801] as compared to other analytical techniques is that several ions may be analyzed simultaneously. One of the most important contributions of cation-exchange chromatography is its sensitivity to ammonium ion, which is difficult to analyze by other techniques [J. Weiss, in: E.L. Johnson (Ed.), Handbook of Ion Chromatography, Dionex, Sunnyvale, CA, USA]. The determination of low concentrations of ammonium ion in the presence of high concentrations of sodium poses a challenge in cation-exchange chromatography [J. Weiss, Ion Chromatography, VCH, 2nd Edition, Weinheim, 1995], as both cations have similar selectivities for the common stationary phases containing either sulfonate or carboxylate functional groups. The task was to develop a new cation-exchange stationary phase (for diverse concentration ratios of adjacent peaks) to overcome limitations experienced in previous trails. Various cation-exchange capacities and column body formats were investigated to optimize this application and others. The advantages and disadvantages of two carboxylic acid columns of different cation-exchange capacities and different column formats will be discussed.

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

    PubMed Central

    Boughlala, Zakaria; Fonseca Guerra, Célia

    2016-01-01

    Abstract We have analyzed the structure and bonding of gas‐phase Cl−X and [HCl−X]+ complexes for X+= H+, CH3 +, Li+, and Na+, using relativistic density functional theory (DFT). We wish to establish a quantitative trend in affinities of the anionic and neutral Lewis bases Cl− and HCl for the various cations. The Cl−X bond becomes longer and weaker along X+ = H+, CH3 +, Li+, and Na+. Our main purpose is to understand the heterolytic bonding mechanism behind the intrinsic (i.e., in the absence of solvent) alkali metal cation affinities (AMCA) and how this compares with and differs from those of the proton affinity (PA) and methyl cation affinity (MCA). Our analyses are based on Kohn–Sham molecular orbital (KS‐MO) theory in combination with a quantitative energy decomposition analysis (EDA) that pinpoints the importance of the different features in the bonding mechanism. Orbital overlap appears to play an important role in determining the trend in cation affinities. PMID:27551660

  15. Sugar Radical Formation by a Proton Coupled Hole Transfer in 2′-Deoxyguanosine Radical Cation (2′-dG•+): A Theoretical Treatment

    PubMed Central

    Kumar, Anil; Sevilla, Michael D.

    2009-01-01

    Previous experimental and theoretical work has established that electronic excitation of a guanine cation radical in nucleosides or in DNA itself leads to sugar radical formation by deprotonation from the dexoxyribose sugar. In this work we investigate a ground electronic state pathway for such sugar radical formation in a hydrated one electron oxidized 2′-deoxyguanosine (dG•+ + 7H2O), using density functional theory (DFT) with the B3LYP functional and the 6-31G* basis set. We follow the stretching of the C5′-H bond in dG•+ to gain an understanding of the energy requirements to transfer the hole from the base to sugar ring and then to deprotonate to proton acceptor sites in solution and on the guanine ring. The geometries of reactant (dG•+ + 7H2O), transition state (TS) for deprotonation of C5′ site and product (dG(•C5′, N7-H+) + 7 H2O) were fully optimized. The zero point energy (ZPE) corrected activation energy (TS) for the proton transfer (PT) from C5′ is calculated to be 9.0 kcal/mol and is achieved by stretching the C5′-H bond by 0.13 Å from its equilibrium bond distance (1.099 Å). Remarkably, this small bond stretch is sufficient to transfer the “hole” (positive charge and spin) from guanine to the C5′ site on the deoxyribose group. Beyond the TS, the proton (H+) spontaneously adds to water to form a hydronium ion (H3O+) as an intermediate. The proton subsequently transfers to the N7 site of the guanine (product). The 9 kcal/mol barrier suggests slow thermal conversion of the cation radical to the sugar radical but also suggests that localized vibrational excitations would be sufficient to induce rapid sugar radical formation in DNA base cation radicals. PMID:19754084

  16. In vitro biopharmaceutical evaluation of ciprofloxacin/metal cation complexes for pulmonary administration.

    PubMed

    Brillault, J; Tewes, F; Couet, W; Olivier, J C

    2017-01-15

    Pulmonary delivery of fluoroquinolones (FQs) is an interesting approach to treat lung infections as it may lead to high local concentrations while minimizing systemic exposure. However, FQs have a rapid diffusion through the lung epithelium giving the pulmonary route no advantage compared to the oral route. Interactions between FQs and metal cations form complexes which limit the diffusion through the epithelial barrier and would reduce the absorption of FQs and maintain high concentrations in the lung. The effects of this complexation depend on the FQ and the metal cations and optimum partners should be selected through in vitro experiments prior to aerosol drug formulation. In this study, CIP was chosen as a representative FQ and 5 cations (Ca 2+ , Mg 2+ , Zn 2+ , Al 3+ , Cu 2+ ) were selected to study the complexation and its effects on permeability, antimicrobial efficacy and cell toxicity. The results showed that the apparent association constants between CIP and cations ranked with the descending order: Cu 2+ >Al 3+ >Zn 2+ >Mg 2+ >Ca 2+ . When a target of 80% complexation was reached with the adequate concentrations of cations, the CIP permeability through the Calu-3 lung epithelial cells was decreased of 50%. Toxicity of the CIP on the Calu-3 cells, with an EC50 evaluated at 7μM, was not significantly affected by the presence of the cations. The minimum inhibitory concentration of CIP for Pseudomonas aeruginosa was not affected or slightly increased in the range of cation concentrations tested, except for Mg 2+ . In conclusion, permeability was the main parameter that was affected by the metal cation complexation while cell toxicity and antimicrobial activity were not or slightly modified. Cu 2+ , with the highest apparent constant of association and with no effect on cell toxicity and antimicrobial activity of the CIP, appeared as a promising cation for the development of a controlled-permeability formulation of CIP for lung treatment. Copyright © 2016

  17. Thermochemical Stability Study of Alkyl-Tethered Quaternary Ammonium Cations for Anion Exchange Membrane Fuel Cells

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

    Mohanty, Angela D.; Tignor, Steven E.; Sturgeon, Matthew R.

    2017-01-01

    The increased interest in the use of anion exchange membranes (AEMs) for applications in electrochemical devices has prompted significant efforts in designing materials with robust stability in alkaline media. Most reported AEMs suffer from polymer backbone degradation as well as cation functional group degradation. In this report, we provide comprehensive experimental investigations for the analysis of cation functional group stability under alkaline media. A silver oxide-mediated ion exchange method and an accelerated stability test in aqueous KOH solutions at elevated temperatures using a Parr reactor were used to evaluate a broad scope of quaternary ammonium (QA) cationic model compound structures,more » particularly focusing on alkyl-tethered cations. Additionally, byproduct analysis was employed to gain better understanding of degradation pathways and trends of alkaline stability. Experimental results under different conditions gave consistent trends in the order of cation stability of various QA small molecule model compounds. Overall, cations that are benzyl-substituted or that are near to electronegative atoms (such as oxygen) degrade faster in alkaline media in comparison to alkyl-tethered QAs. These comprehensive model compound stability studies provide valuable information regarding the relative stability of various cation structures and can help guide researchers towards designing new and promising candidates for AEM materials.« less

  18. Formation of RNA oligomers on montmorillonite: site of catalysis

    NASA Technical Reports Server (NTRS)

    Ertem, G.; Ferris, J. P.

    1998-01-01

    Certain montmorillonites catalyze the self condensation of the 5'-phosphorimidazolide of nucleosides in pH 8 aqueous electrolyte solutions at ambient temperatures leading to formation of RNA oligomers. In order to establish the nature of the sites on montmorillonite responsible for this catalytic activity, oligomerization reactions were run with montmorillonites which had been selectively modified (I) at the edges by (a) fluoride treatment, (b) silylation, (c) metaphosphate treatment of the anion exchange sites (II) in the interlayer by (a) saturation with quaternary alkylammonium ions of increasing size, (b) aluminum polyoxo cations. High pressure liquid chromatography, HPLC, analysis of condensation products for their chain lengths and yields indicated that modification at the edges did not affect the catalytic activity to a significant extent, while blocking the interlayer strongly inhibited product formation.

  19. Substantiating In Vivo Magnetic Brain Tumor Targeting of Cationic Iron Oxide Nanocarriers via Adsorptive Surface Masking

    PubMed Central

    Chertok, Beata; David, Allan E.; Moffat, Bradford A.; Yang, Victor C.

    2009-01-01

    Cationic magnetic nanoparticles are attractive as potential vehicles for tumor drug delivery due to their favorable interactions with both the tumor milieu and the therapeutic cargo. However, systemic delivery of these nanoparticles to the tumor site is compromised by their rapid plasma clearance. We developed a simple method for in vivo protection of cationic nanocarriers, using non-covalent surface masking with a conjugate of low molecular weight heparin and polyethylene glycol. Surface masking resulted in an 11-fold increase in plasma AUC and a 2-fold increase in the magnetic capture of systemically injected nanoparticles in orthotopic rodent brain tumors. Overall, the described methodology could expand the prospective applications for cationic magnetic nanoparticles in magnetically-mediated gene/drug delivery. PMID:19782394

  20. Microdomain Formation, Oxidation, and Cation Ordering in LaCa 2Fe 3O 8+y

    DOE PAGES

    Price, Patrick M.; Browning, Nigel D.; Butt, Darryl P.

    2015-03-23

    The compound LaCa 2Fe 3O 8+y, also known as the Grenier phase, is known to undergo an order-disorder transformation (ODT) at high temperatures. Oxidation has been observed when the compound is cooled in air after the ODT. In this study, we have synthesized the Grenier compound in air using traditional solid state reactions and investigated the structure and composition before and after the ODT. Thermal analysis showed that the material undergoes an order-disorder transformation in both oxygen and argon atmospheres with dynamic, temperature dependent, oxidation upon cooling. Results from scanning transmission electron microscopy (STEM) suggest that the Grenier phase hasmore » preferential segregation of Ca and La on the two crystallographic A-sites before the ODT, but a random distribution above the ODT temperature. Furthermore, STEM images suggest the possibility that oxygen excess may exist in La-rich regions within microdomains rather than at microdomain boundaries.« less

  1. Interaction of In(I) and Tl(I) cations with 2,6-diaryl pyridine ligands: cation encapsulation within a very weakly interacting N/arene host environment.

    PubMed

    Mansaray, Hassanatu B; Tang, Christina Y; Vidovic, Dragoslav; Thompson, Amber L; Aldridge, Simon

    2012-12-03

    The interaction of 2,6-dimesitylpyridine with Tl(I) and In(I) cations has been investigated with a view to developing tractable molecular M(I) compounds which are soluble in organic media. In stark contrast to isosteric and isoelectronic terphenyl systems, complexes featuring the [(2,6-Mes(2)py)M](+) fragment feature very weak metal-ligand interactions in the solid state, as revealed by M-N distances of the order of 2.45 Å (M = In) and 2.64 Å (M = Tl). While additional weak π interactions are observed with arene solvate molecules in these systems, the related 2:1 complex [(2,6-Mes(2)py)(2)In][BAr(f)(4)] features an In(I) center wholly encapsulated by the bulky Mes(2)py donors, and even longer In-N distances [2.586(6) and 2.662(5) Å]. These contacts are about 0.5 Å greater than the sum of the respective covalent radii (2.13 Å) and provide evidence for an effectively "naked" In(I) cation stabilized to a minor extent by orbital interactions.

  2. [PAH Cations as Viable Carriers of DIBs

    NASA Technical Reports Server (NTRS)

    Snow, Ted

    1998-01-01

    This report is intended to fill in the blanks in NASA's file system for our lab astro study of molecular ions of astrophysical interest. In order to give NASA what it needs for its files, I attach below the text of the section from our recent proposal to continue this work, in which we describe progress to date, including a large number of publications. Our initial studies were focused on PAH cations, which appear to be viable candidates as the carriers of the DIBs, an idea that has been supported by laboratory spectroscopy of PAH cations in inert matrices. Beginning with the simplest aromatic (benzene; C6H6) and moving progressively to larger species (naphthalene, C10OH8; pyrene, C16H10; and most recently chrysene, C18H12), we have been able to derive rate coefficients for reactions with neutral spices that are abundant in the diffuse interstellar medium.

  3. Solid-state NMR study of various mono- and divalent cation forms of the natural zeolite natrolite.

    PubMed

    Park, Min Bum; Vicente, Aurélie; Fernandez, Christian; Hong, Suk Bong

    2013-05-28

    Here we present the one-dimensional (29)Si and (27)Al MAS NMR and two-dimensional (27)Al MQMAS and DQF-STMAS NMR spectra of the monovalent (Na(+), K(+), Rb(+), Cs(+) and NH4(+)) and divalent (Ca(2+), Sr(2+) and Ba(2+)) cation forms of the natural zeolite natrolite (framework type NAT) with complete Si-Al ordering over the crystallographically distinct tetrahedral sites and with the same hydration state (hydrated, partially dehydrated or fully dehydrated). In the case of monovalent cation-exchanged natrolites, the differences in their crystal symmetry evidenced by (29)Si MAS NMR were found to be in good agreement with those determined by crystallographic analyses. However, (27)Al DQF-STMAS NMR spectroscopy shows the presence of two distinct Al sites in dehydrated K-NAT, Rb-NAT and NH4-NAT, suggesting that their actual crystal symmetry is lower than the reported one (i.e., orthorhombic Fdd2). The MAS NMR results also show that the space group of hydrated Ca-NAT is lower than that (monoclinic F1d1) of hydrated scolecite, the natural calcium counterpart of natrolite, which is also the case with hydrated Sr-NAT and Ba-NAT. We believe that the unexpected diversity in the crystal symmetry of natrolite caused by exchange of various mono- and divalent ions, as well as by dehydration, may be inherently due to the high framework flexibility of this natural zeolite.

  4. Cation-dependent nutrient transport in shrimp digestive tract.

    PubMed

    Simmons, Tamla; Mozo, Julie; Wilson, Jennifer; Ahearn, Gregory A

    2012-02-01

    Purified epithelial brush border membrane vesicles (BBMV) were produced from the hepatopancreas of the Atlantic White shrimp, Litopeneaus setiferus, using standard methods originally developed for mammalian tissues and previously applied to other crustacean and echinoderm epithelia. These vesicles were used to study the cation dependency of sugar and amino acid transport across luminal membranes of hepatopancreatic epithelial cells. (3)H-D: -glucose uptake by BBMV against transient sugar concentration gradients occurred when either transmembrane sodium or potassium gradients were the only driving forces for sugar accumulation, suggesting the presence of a possible coupled transport system capable of using either cation. (3)H-L: -histidine transport was only stimulated by a transmembrane potassium gradient, while (3)H-L: -leucine uptake was enhanced by either a sodium or potassium gradient. These responses suggest the possible presence of a potassium-dependent transporter that accommodates either amino acid and a sodium-dependent system restricted only to L: -leucine. Uptake of (3)H-L: -leucine was significantly stimulated (P < 0.05) by several metallic cations (e.g., Zn(2+), Cu(2+), Mn(2+), Cd(2+), or Co(2+)) at external pH values of 7.0 or 5.0 (internal pH 7.0), suggesting a potential synergistic role of the cations in the transmembrane transfer of amino acids. (3)H-L: -histidine influxes (15 suptakes) were hyperbolic functions of external [zinc] or [manganese], following Michaelis-Menten kinetics. The apparent affinity constant (e.g., K (m)) for manganese was an order of magnitude smaller (K (m) = 0.22 μM Mn) than that for zinc (K (m) = 1.80 μM Zn), while no significant difference (P > 0.05) occurred between their maximal transport velocities (e.g., J (max)). These results suggest that a number of cation-dependent nutrient transport systems occur on the shrimp brush border membrane and aid in the absorption of these important dietary elements.

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

    PubMed

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

    2017-11-07

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

  6. A Family of A-Site Cation-Deficient Double-Perovskite-Related Iridates: Ln9Sr2Ir4O24 (Ln = La, Pr, Nd, Sm).

    PubMed

    Ferreira, Timothy; Smith, Mark D; Zur Loye, Hans-Conrad

    2018-06-21

    The compositions of the general formula Ln 11- x Sr x Ir 4 O 24 (Ln = La, Pr, Nd, Sm; 1.37 ≥ x ≥ 2) belonging to a family of A-site cation-deficient double-perovskite-related oxide iridates were grown as highly faceted single crystals from a molten strontium chloride flux. Their structures were determined by single-crystal X-ray diffraction. On the basis of the single-crystal results, additional compositions, Ln 9 Sr 2 Ir 4 O 24 (Ln = La, Pr, Nd, Sm), were prepared as polycrystalline powders via solid-state reactions and structurally characterized by Rietveld refinement. The compositions Ln 9 Sr 2 Ir 4 O 24 (Ln = La, Pr, Nd, Sm) contain Ir(V) and Ir(IV) in a 1:3 ratio with an average iridium oxidation state of 4.25. The single-crystal compositions La 9.15 Sr 1.85 Ir 4 O 24 and Pr 9.63 Sr 1.37 Ir 4 O 24 contain relatively less Ir(V), with the average iridium oxidation states being 4.21 and 4.09, respectively. The magnetic properties of Ln 9 Sr 2 Ir 4 O 24 (Ln = La, Pr, Nd, Sm) were measured, and complex magnetic behavior was observed in all cases at temperatures below 30 K.

  7. Development of a stable cation modified graphene oxide membrane for water treatment

    NASA Astrophysics Data System (ADS)

    Yu, Wenzheng; (Yet Yu, Tong; Graham, Nigel

    2017-12-01

    Membranes prepared from layers of graphene oxide (GO) offer substantial advantages over conventional materials for water treatment (e.g. greater flux), but the stability of GO membranes in water has not been achieved until now. In this study the behavior of GO membranes prepared with different quantities and species of cations has been investigated to establish the feasibility of their application in water treatment. A range of cation-modified GO membranes were prepared and exposed to aqueous solutions containing specific chemical constituents. In pure water, unmodified and Na-modified GO membranes were highly unstable, while GO membranes modified with multivalent cations were stable provided there were sufficient quantities of cations present; their relative capability to achieve GO stability was as follows: Al3+  >  Ca2+  >  Mg2+  >  Na+. It is believed that the mechanism of cross-linking, and membrane stability, is via metal-carboxylate chelates and cation-graphite surface interactions (cation-π interaction), and that the latter appears to increase with increasing cation valency. The instability of cation (Ca or Al)-modified GO membranes by NaCl solutions during permeation occurred as Na+ exchanged with the incorporated multivalent cations, but a high content of Al3+ in the GO membrane impeded Al3+/Na+ exchange and thus retained membrane stability. In solutions containing biopolymers representative of surface waters or seawater (protein and polysaccharide solutions), Ca-GO membranes (even with high Ca2+ content) were not stable, while Al-GO membranes were stable if the Al3+ content was sufficiently high; Al-formed membranes also had a greater flux than Ca-GO membranes.

  8. Characterization of Highly Sulfonated SIBS Polymer Partially Neutralized With Mg(+2) Cations

    DTIC Science & Technology

    2008-08-01

    protective clothing, block copolymer ionomer membranes emerge. They are highly ordered sequence of both ionic and nonionic blocks, in which the ionic ...incorporated into the ionic polymer. Fourier-transform infrared spectroscopy results revealed that a significant amount of ordering occurred as a result on...increasing Mg content. This band indicates Mg complexation formed when two or more sulfonate groups ionically bonded to the Mg+2 cation

  9. High-pressure behavior of A 2 B 2 O 7 pyrochlore (A=Eu, Dy; B=Ti, Zr)

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

    Rittman, Dylan R.; Turner, Katlyn M.; Park, Sulgiye

    2017-01-28

    In situ high-pressure X-ray diffraction and Raman spectroscopy were used to determine the influence of composition on the high-pressure behavior of A 2B 2O 7 pyrochlore (A=Eu, Dy; B=Ti, Zr) up to ~50GPa. Based on X-ray diffraction results, all compositions transformed to the high-pressure cotunnite structure. The B-site cation species had a larger effect on the transition pressure than the A-site cation species, with the onset of the phase transformation occurring at ~41 GPa for B=Ti and ~16 GPa B=Zr. However, the A-site cation affected the kinetics of the phase transformation, with the transformation for compositions with the smaller ionicmore » radii, i.e., A=Dy, proceeding faster than those with a larger ionic radii, i.e., A=Eu. These results were consistent with previous work in which the radius-ratio of the A- and B-site cations determined the energetics of disordering, and compositions with more similarly sized A- and B-site cations had a lower defect formation energy. Raman spectra revealed differences in the degree of short-range order of the different compositions. Due to the large phase fraction of cotunnite at high pressure for B=Zr compositions, Raman modes for cotunnite could be observed, with more modes recorded for A=Eu than A=Dy. These additional modes are attributed to increased short-to-medium range ordering in the initially pyrochlore structured Eu 2Zr 2O 7 as compared with the initially defect-fluorite structured Dy 2Zr 2O 7.« less

  10. Tetracycline adsorption on kaolinite: pH, metal cations and humic acid effects.

    PubMed

    Zhao, Yanping; Geng, Jinju; Wang, Xiaorong; Gu, Xueyuan; Gao, Shixiang

    2011-07-01

    Contamination of environmental matrixes by human and animal wastes containing antibiotics is a growing health concern. Because tetracycline is one of the most widely-used antibiotics in the world, it is important to understand the factors that influence its mobility in soils. This study investigated the effects of pH, background electrolyte cations (Li(+), Na(+), K(+), Ca(2+) and Mg(2+)), heavy metal Cu(2+) and humic acid (HA) on tetracycline adsorption onto kaolinite. Results showed that tetracycline was greatly adsorbed by kaolinite over pH 3-6, then decreased with the increase of pH, indicating that tetracycline adsorption mainly through ion exchange of cations species and complexation of zwitterions species. In the presence of five types of cations (Li(+), Na(+), K(+), Ca(2+) and Mg(2+)), tetracycline adsorption decreased in accordance with the increasing of atomic radius and valence of metal cations, which suggested that outer-sphere complexes formed between tetracycline and kaolinite, and the existence of competitor ions lead to the decreasing adsorption. The presence of Cu(2+) greatly enhanced the adsorption probably by acting as a bridge ion between tetracycline species and the edge sites of kaolinite. HA also showed a major effect on the adsorption: at pH < 6, the presence of HA increased the adsorption, while the addition of HA showed little effect on tetracycline adsorption at higher pH. The soil environmental conditions, like pH, metal cations and soil organic matter, strongly influence the adsorption behavior of tetracycline onto kaolinite and need to be considered when assessing the environmental toxicity of tetracycline.

  11. Structural evolution of the double perovskites Sr{sub 2}B'UO{sub 6} (B' = Mn, Fe, Co, Ni, Zn) upon reduction: Magnetic behavior of the uranium cations

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

    Pinacca, R.M., E-mail: rmp@unsl.edu.ar; Viola, M.C.; Pedregosa, J.C.

    2011-11-15

    Highlights: {yields} Evolution of the double perovskites Sr{sub 2}B'UO{sub 6} upon reduction were studied by XRPD. {yields} Orthorhombic (Pnma) disordered perovskites SrB'{sub 0.5-x}U{sub 0.5+x}O{sub 3} were obtained at 900 {sup o}C. {yields} U{sup 5+/4+} and Zn{sup 2+} cations are distributed at random over the octahedral positions. {yields} AFM ordering for the perovskite with B' = Zn appears below 30 K. -- Abstract: We describe the preparation of five perovskite oxides obtained upon reduction of Sr{sub 2}B'UO{sub 6} (B' = Mn, Fe, Co, Ni, Zn) with H{sub 2}/N{sub 2} (5%/95%) at 900 {sup o}C during 8 h, and their structural characterizationmore » by X-ray powder diffraction (XRPD). During the reduction process there is a partial segregation of the elemental metal when B' = Co, Ni, Fe, and the corresponding B'O oxide when B' = Mn, Zn. Whereas the parent, oxygen stoichiometric double perovskites Sr{sub 2}B'UO{sub 6} are long-range ordered concerning B' and U cations. The crystal structures of the reduced phases, SrB'{sub 0.5-x}U{sub 0.5+x}O{sub 3} with 0.37 < x < 0.27, correspond to simple, disordered perovskites; they are orthorhombic, space group Pnma (No. 62), with a full cationic disorder at the B site. Magnetic measurements performed on the phase with B' = Zn, indicate uncompensated antiferromagnetic ordering of the U{sup 5+}/U{sup 4+} sublattice below 30 K.« less

  12. Stressor states and the cation crossroads.

    PubMed

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

    2010-12-01

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

  13. The Rubella Virus Nonstructural Protease Requires Divalent Cations for Activity and Functions in trans

    PubMed Central

    Liu, Xin; Ropp, Susan L.; Jackson, Richard J.; Frey, Teryl K.

    1998-01-01

    The rubella virus (RUB) nonstructural (NS) protease is a papain-like cysteine protease (PCP) located in the NS-protein open reading frame (NSP-ORF) that cleaves the NSP-ORF translation product at a single site to produce two products, P150 (the N-terminal product) and P90 (the C-terminal product). The RUB NS protease was found not to function following translation in vitro in a standard rabbit reticulocyte lysate system, although all of the other viral PCPs do so. However, in the presence of divalent cations such as Zn2+, Cd2+, and Co2+, the RUB NS protease functioned efficiently, indicating that these cations are required either as direct cofactors in catalytic activity or for correct acquisition of three-dimensional conformation of the protease. Since other viral and cell PCPs do not require cations for activity and the RUB NS protease contains a putative zinc binding motif, the latter possibility is more likely. Previous in vivo expression studies of the RUB NS protease failed to demonstrate trans cleavage activity (J.-P. Chen et al., J. Virol. 70:4707–4713, 1996). To study whether trans cleavage could be detected in vitro, a protease catalytic site mutant and a mutant in which the C-terminal 31 amino acids of P90 were deleted were independently introduced into plasmid constructs that express the complete NSP-ORF. Cotranslation of these mutants in vitro yielded both the native and the mutated forms of P90, indicating that the protease present in the mutated construct cleaved the catalytic-site mutant precursor. Thus, RUB NS protease can function in trans. PMID:9557742

  14. Cation radius effects on the helix-coil transition of DNA. Cryptates and other large cations.

    PubMed Central

    Trend, B L; Knoll, D A; Ueno, M; Evans, D F; Bloomfield, V A

    1990-01-01

    Most polyelectrolyte theories of the effect of ions on the thermal melting of DNA assume that the predominant influence of the cations comes through their charge. Ion size and structure are treated, for analytic convenience, as negligible variables. We have examined the validity of this assumption by measuring the melting temperature of calf thymus DNA as a function of salt concentration with four univalent cations of different hydrated radii. These are K+ (3.3 A), (n-Pr)4N+ (4.5 A), (EtOH)4N+ (4.5 A), and C222-K+ (5 A). C222-K+ is a complex of cryptand C222 with K+. With K+ as the sole cation, Tm varies linearly with the log of ionic strength over the range 0.001-0.1 M. With all the K+ sequestered by an equimolar amount of C222, Tm is depressed by 10-20 degrees C and the slope of Tm vs. ionic strength is lower. At low ionic strength, an even greater reduction in Tm is achieved with (n-Pr)4N+; but the similar-sized (EtOH)4N+ gives a curve more similar to K+. Theoretical modeling, taking into account cation size through the Poisson-Boltzmann equation for cylindrical polyelectrolytes, predicts that larger cations should be less effective in stabilizing the double helix; but the calculated effect is less than observed experimentally. These results show that valence, cation size, and specific solvation effects are all important in determining the stability of the double-helical form of DNA. PMID:2344467

  15. Ability of a montmorillonitic clay to interact with cationic and anionic dyes in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Pleşa Chicinaş, R.; Bedelean, H.; Stefan, R.; Măicăneanu, A.

    2018-02-01

    A montmorillonitic clay in raw and treated forms (size-fractionated, organoclay, Al pillared) was evaluated as adsorbent for cationic (toluidine blue - TB and malachite green - MG) and anionic (Congo red - CR) dyes. A thorough characterization using XRD, SEM-EDS, N2 adsorption, and FTIR of the considered samples was realized, all highlighting the structural changes after various treatments. UV-VIS analysis demonstrated the interaction between dyes and the adsorbent surface. The investigation of the effects of various experimental parameters using a batch adsorption technique showed that ON has a high adsorption potential for cationic dyes (33 and 39 mg/g in case of TB and MG, respectively). The kinetic study indicated that the adsorption process followed the pseudo-second-order model, while Freundlich isotherm showed a favorable adsorption. The calculated values of Gibbs free energy suggested also that the adsorption is spontaneous and is more favorable at higher temperatures.

  16. Cation-π interaction of the univalent sodium cation with [2.2.2]paracyclophane: Experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Makrlík, Emanuel; Sýkora, David; Böhm, Stanislav; Vaňura, Petr

    2018-02-01

    By employing electrospray ionization mass spectrometry (ESI-MS), it was proven experimentally that the univalent sodium cation (Na+) forms with [2.2.2]paracyclophane (C24H24) the cationic complex [Na(C24H24)]+. Further, applying quantum chemical DFT calculations, the most probable structure of the [Na(C24H24)]+ complex was derived. In the resulting complex with a symmetry very close to C3, the "central" cation Na+, fully located in the cavity of the parent [2.2.2]paracyclophane ligand, is bound to all three benzene rings of [2.2.2]paracyclophane via cation-π interaction. Finally, the interaction energy, E(int), of the considered cation-π complex [Na(C24H24)]+ was found to be -267.3 kJ/mol, confirming the formation of this fascinating complex species as well.

  17. Pb(B{sup {prime}}{sub 1/2}B{sup {prime}{prime}}{sub 1/2})O{sub 3}-type perovskites: Part II. Short-range order parameter as a criterion of the distinction between relaxor and normal ferroelectrics

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

    Kim, S.; Jang, H.M.

    1997-08-01

    A classification scheme of Pb(B{sup {prime}}{sub 1/2}B{sup {prime}{prime}}{sub 1/2})O{sub 3}-type perovskites with respect to the B-site order parameters was proposed based on the theoretical calculation of the short-range order parameter ({sigma}) using the pair-correlation model. The calculated order parameters predict that a Pb(B{sup {prime}}{sub 1/2}B{sup {prime}{prime}}{sub 1/2})O{sub 3}-type perovskite without any charge difference between B{sup {prime}} and B{sup {prime}{prime}} cations [e.g., Pb(Zr{sub 1/2}Ti{sub 1/2})O{sub 3} (PZT)] is represented by a completely disordered state with the absence of a finite coherence length. On the other hand, a Pb(B{sup {prime}}{sub 1/2}B{sup {prime}{prime}}{sub 1/2})O{sub 3} type perovskite system having different ionic charges ismore » characterized either by the short-range ordering with a nanoscale coherence length or by the macroscopic long-range ordering, depending on the magnitude of ionic charge difference between B{sup {prime}} and B{sup {prime}{prime}} ions. The normal ferroelectricity in Pb(B{sup {prime}}{sub 1/2}B{sup {prime}{prime}}{sub 1/2})O{sub 3}-type complex perovskites was then correlated either with a completely disordered state ({sigma}=0) or with a perfectly ordered state ({sigma}=1), whereas the relaxor behavior was attributed to the nanoscale short-range ordering (0{lt}{sigma}{lt}1) in the configuration of the B-site cations. {copyright} {ital 1997 Materials Research Society.}« less

  18. Cation Radical Accelerated Nucleophilic Aromatic Substitution via Organic Photoredox Catalysis.

    PubMed

    Tay, Nicholas E S; Nicewicz, David A

    2017-11-15

    Nucleophilic aromatic substitution (S N Ar) is a direct method for arene functionalization; however, it can be hampered by low reactivity of arene substrates and their availability. Herein we describe a cation radical-accelerated nucleophilic aromatic substitution using methoxy- and benzyloxy-groups as nucleofuges. In particular, lignin-derived aromatics containing guaiacol and veratrole motifs were competent substrates for functionalization. We also demonstrate an example of site-selective substitutive oxygenation with trifluoroethanol to afford the desired trifluoromethylaryl ether.

  19. Can Fe3+ and Al3+ ions serve as cationic bridges to facilitate the adsorption of anionic As(V) species on humic acids? A density functional theory study.

    PubMed

    Gorb, Leonid; Shukla, Manoj K

    2017-03-01

    A computational chemistry investigation was undertaken to shed light on the facilitatory role played by Fe 3+ and Al 3+ cations in the adsorption of anionic As(V) species by humic acids through the formation of so-called cationic bridges. Geometric and energetic parameters were obtained using density functional theory at the B3LYP/6-31G(d,p) level in conjunction with the polarizable continuum model (to account for the influence of bulk water). We found that, despite their similar molecular geometries, the adsorption energies of the As(V) species AsO 4 3- and H 2 AsO 4- differ when Fe 3+ , FeOH 2+ , Al 3+ , and AlOH 2+ participate in the bridge. We also found that effective adsorption of As(V) species by humic acids strongly depends on whether the considered cationic bridges are tightly coordinated by humic acids at the adsorption sites, as well as on the rigidity of these humic acid adsorption sites.

  20. Influence of lithium cations on prolyl peptide bonds.

    PubMed

    Kunz, Claudia; Jahreis, Günther; Günther, Robert; Berger, Stefan; Fischer, Gunter; Hofmann, Hans-Jörg

    2012-06-01

    The influence of lithium cations on the cis/trans isomerization of prolyl peptide bonds was investigated in a quantitative manner in trifluoroethanol (TFE) and acetonitrile, employing NMR techniques. The focus was on various environmental and structural aspects, such as lithium cation and water concentrations, the type of the partner amino acid in the prolyl peptide bond, and the peptide sequence length. Comparison of the thermodynamic parameters of the isomerization in LiCl/TFE and TFE shows a lithium cation concentration dependence of the cis/trans ratio, which saturates at cation concentrations >200 mM. A pronounced increase in the cis isomer content in the presence of lithium cations occurs with the exception of peptides with Gly-Pro and Asp-Pro moieties. The cation effect appears already at the dipeptide level. The salt concentration can considerably be reduced in solvents with a lower number of nucleophilic centers like acetonitrile. The lithium cation effect decreases with small amounts of water and disappears at a water concentration of about 5%. The isomerization kinetics under the influence of lithium cations suggests a weak cation interaction with the carbonyl oxygen of the peptide bond. Copyright © 2012 European Peptide Society and John Wiley & Sons, Ltd.

  1. 77 FR 58868 - Public Land Order No. 7798; Partial Modification of Power Site Classification No. 126; Washington

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-09-24

    ...; WAOR-19641] Public Land Order No. 7798; Partial Modification of Power Site Classification No. 126... partially modifies a withdrawal which established Power Site Classification No. 126, insofar as it affects... under Power Site Classification No. 126 for water power purposes will not be injured by U.S. Forest...

  2. Cation Distribution and Local Configuration of Fe 2+ Ions in Structurally Nonequivalent Lattice Sites of Heterometallic Fe(II)/ M(II) ( M = Mn, Co, Ni, Cu, Zn) Diaquadiformato Complexes

    NASA Astrophysics Data System (ADS)

    Devillers, M.; Ladrière, J.

    1993-03-01

    57Fe Mössbauer investigations are carried out on a wide series of heterometallic diaquadiformato Fe(II)/ M(II) complexes with M = Mn, Co, Ni, Cu, and Zn to provide a local picture of the coordination environment of the 57Fe 2+ ions as a function of (i) the nature of the host cation and (ii) the relative amounts of both metals in the matrix (between 50 and 0.25 at.% Fe). Information is obtained on the quantitative distribution of both metals between the two structurally nonequivalent lattice sites and on the local geometry around the dopant atom in each crystal site. In the mixed Fe-Cu complexes. Fe 2+ ions are preferentially incorporated in the tetrahydrated site; in Cu-rich Fe xCu 1- x(HCO 2) 2· 2H 2O, the 57Fe 2+ ions located in the hexaformato-coordinated site are surrounded by an axially compressed octahedron of formate ligands which contrasts with the elongated configuration observed in the pure iron compound and in the other mixed systems. Semiquantitative estimations of the tetragonal field splitting and of the extent of metal-ligand interactions are proposed from the temperature dependence of the quadrupole splitting values.

  3. Enzyme architecture: optimization of transition state stabilization from a cation-phosphodianion pair.

    PubMed

    Reyes, Archie C; Koudelka, Astrid P; Amyes, Tina L; Richard, John P

    2015-04-29

    The side chain cation of R269 lies at the surface of l-glycerol 3-phosphate dehydrogenase (GPDH) and forms an ion pair to the phosphodianion of substrate dihydroxyacetone phosphate (DHAP), which is buried at the nonpolar protein interior. The R269A mutation of GPDH results in a 110-fold increase in K(m) (2.8 kcal/mol effect) and a 41,000-fold decrease in k(cat) (6.3 kcal/mol effect), which corresponds to a 9.1 kcal/mol destabilization of the transition state for GPDH-catalyzed reduction of DHAP by NADH. There is a 6.7 kcal/mol stabilization of the transition state for the R269A mutant GPDH-catalyzed reaction by 1.0 M guanidinium ion, and the transition state for the reaction of the substrate pieces is stabilized by an additional 2.4 kcal/mol by their covalent attachment at wildtype GPDH. These results provide strong support for the proposal that GPDH invests the 11 kcal/mol intrinsic phosphodianion binding energy of DHAP in trapping the substrate at a nonpolar active site, where strong electrostatic interactions are favored, and obtains a 9 kcal/mol return from stabilizing interactions between the side chain cation and transition state trianion. We propose a wide propagation for the catalytic motif examined in this work, which enables strong transition state stabilization from enzyme-phosphodianion pairs.

  4. Cationic uremic toxins affect human renal proximal tubule cell functioning through interaction with the organic cation transporter.

    PubMed

    Schophuizen, Carolien M S; Wilmer, Martijn J; Jansen, Jitske; Gustavsson, Lena; Hilgendorf, Constanze; Hoenderop, Joost G J; van den Heuvel, Lambert P; Masereeuw, Rosalinde

    2013-12-01

    Several organic cations, such as guanidino compounds and polyamines, have been found to accumulate in plasma of patients with kidney failure due to inadequate renal clearance. Here, we studied the interaction of cationic uremic toxins with renal organic cation transport in a conditionally immortalized human proximal tubule epithelial cell line (ciPTEC). Transporter activity was measured and validated in cell suspensions by studying uptake of the fluorescent substrate 4-(4-(dimethylamino)styryl)-N-methylpyridinium-iodide (ASP(+)). Subsequently, the inhibitory potencies of the cationic uremic toxins, cadaverine, putrescine, spermine and spermidine (polyamines), acrolein (polyamine breakdown product), guanidine, and methylguanidine (guanidino compounds) were determined. Concentration-dependent inhibition of ASP(+) uptake by TPA, cimetidine, quinidine, and metformin confirmed functional endogenous organic cation transporter 2 (OCT2) expression in ciPTEC. All uremic toxins tested inhibited ASP(+) uptake, of which acrolein required the lowest concentration to provoke a half-maximal inhibition (IC50 = 44 ± 2 μM). A Dixon plot was constructed for acrolein using three independent inhibition curves with 10, 20, or 30 μM ASP(+), which demonstrated competitive or mixed type of interaction (K i = 93 ± 16 μM). Exposing the cells to a mixture of cationic uremic toxins resulted in a more potent and biphasic inhibitory response curve, indicating complex interactions between the toxins and ASP(+) uptake. In conclusion, ciPTEC proves a suitable model to study cationic xenobiotic interactions. Inhibition of cellular uptake transport was demonstrated for several uremic toxins, which might indicate a possible role in kidney disease progression during uremia.

  5. New cation-exchange material based on a sulfonated 3,4-ethylenedioxythiophene monomer

    NASA Astrophysics Data System (ADS)

    Stéphan, O.; Schottland, P.; Le Gall, P.-Y.; Chevrot, C.

    1998-06-01

    The electrochemical oxidation, in aqueous medium, of a 3,4-ethylenedioxythiophene monomer functionalized by a sulfonate group exhibiting cation-exchange properties, allows the synthesis of a new type of water-soluble material. In order to synthesize in water, by oxidative electropolymerization, polymer films of controlled thickness containing attached sulfonate groups, we have investigated the polymerization of the functionalized monomer in the presence of the unsubstituted one without supporting electrolyte. Using an equimolar mixture (0.01 mol/l) of both monomers, copolymers exhibiting cation exchange abilities have been synthesized. As an example, th easy incorporation of hexaamine-ruthenium(III) into one of these copolymers is briefly reported. L'oxydation électrochimique en milieu aqueux d'un monomère de type 3,4- éthylènedioxythiophène fonctionnalisé par un groupement sulfonate permet d'envisager la synthèse d'un nouveau type de polymère hydrosoluble. Afin d'obtenir électrochimiquement en milieu aqueux, un film de polymère d'épaisseur contrôlée contenant des groupements sulfonates, nous avons evisagé de polymériser ce monomère en présence de son homologue non substitué. En partant d'un mélange équimolaire (0.01 mol/l) des deux monomères et en l'absence d'électrolyte support, nous avons synthétisé un matériau possédant des propriétés d'échange de cations. A titre d'exemple, nous présentons brièvement l'incorporation d'un complexe hexaaminé du ruthénium(III) dans un de ces copolymères.

  6. Structure and oil responsiveness of viscoelastic fluids based on mixed anionic/cationic wormlike surfactant micelles

    NASA Astrophysics Data System (ADS)

    Shibaev, A. V.; Makarov, A. V.; Aleshina, A. L.; Rogachev, A. V.; Kuklin, A. I.; Philippova, O. E.

    2017-05-01

    In this work, a combination of small-angle neutron scattering, dynamic light scattering and rheometry was applied in order to investigate the structure and oil responsiveness of anionic/cationic wormlike surfactant micelles formed in a mixture of potassium oleate and n-octyltrimethylammonium bromide (C8TAB). A new facile method of calculating the structure factor of charged interacting wormlike micelles was proposed. It was shown that the mean distance between the micelles decreases upon the increase of the amount of cationic co-surfactant and lowering of the net micellar charge. It was demonstrated that highly viscous fluids containing mixed anionic/cationic wormlike micelles are highly responsive to oil due to its solubilization inside the micellar cores, which leads to the disruption of micelles and formation of microemulsion droplets. Experimental data suggest that solubilization of oil proceeds differently in the case of mixed anionic/cationic micelles in the absence of salt, and anionic micelles of the same surfactant in the presence of KCl.

  7. Quantum Simulation of Helium Hydride Cation in a Solid-State Spin Register.

    PubMed

    Wang, Ya; Dolde, Florian; Biamonte, Jacob; Babbush, Ryan; Bergholm, Ville; Yang, Sen; Jakobi, Ingmar; Neumann, Philipp; Aspuru-Guzik, Alán; Whitfield, James D; Wrachtrup, Jörg

    2015-08-25

    Ab initio computation of molecular properties is one of the most promising applications of quantum computing. While this problem is widely believed to be intractable for classical computers, efficient quantum algorithms exist which have the potential to vastly accelerate research throughput in fields ranging from material science to drug discovery. Using a solid-state quantum register realized in a nitrogen-vacancy (NV) defect in diamond, we compute the bond dissociation curve of the minimal basis helium hydride cation, HeH(+). Moreover, we report an energy uncertainty (given our model basis) of the order of 10(-14) hartree, which is 10 orders of magnitude below the desired chemical precision. As NV centers in diamond provide a robust and straightforward platform for quantum information processing, our work provides an important step toward a fully scalable solid-state implementation of a quantum chemistry simulator.

  8. Cation Movements during Dehydration and NO2 Desorption in a Ba-Y,FAU zeolite: an in situ Time-resolved X-ray Diffraction Study

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

    Wang, Xianqin; Hanson, Jonathan C.; Kwak, Ja Hun

    2013-02-28

    Synchrotron-based in situ time-resolved X-ray diffraction and Rietveld analysis were used to probe the interactions between BaY, FAU zeolite frameworks and H2O or NO2 molecules. These results provided information about the migration of the Ba2+ cations in the zeolite framework during dehydration and during NO2 adsorption/desorption processes in a water free zeolite. In the hydrated structure water molecules form four double rings of hexagonal ice-like clusters [(H2O)6] in the 12-ring openings of the super-cage. These water rings interacted with the cations and the zeolite framework through four cation/water clusters centered over the four 6-membered rings of the super-cage (site II).more » Interpenetrating tetrahedral water clusters [(H2O)4] and tetrahedral Ba+2 cation clusters were observed in the sodalite cage. Consistent with the reported FT-IR results, three different ionic NOx species (NO+, NO+-NO2, and NO3-) were observed following NO2 adsorption by the dehydrated Ba-Y,FAU zeolite. The structure of the water and the NOx species were correlated with the interactions between the adsorbates, the cations, and the framework. The population of Ba2+ ions at different cationic positions strongly depended on the amount of bound water or NOx species. Both dehydration and NO2 adsorption/desorption resulted in facile migration of Ba2+ ions among the different cationic positions. Data obtained in this work have provided direct evidence for the Ba2+ cation migration to accommodate the binding of gas molecules. This important feature may play a pivotal role in the strong binding of NO2 to Ba-Y,FAU zeolite, a prerequisite for high catalytic activity in lean NOx reduction catalysis.« less

  9. Imidazolium Cations with Exceptional Alkaline Stability: A Systematic Study of Structure–Stability Relationships

    DOE PAGES

    Hugar, Kristina M.; Kostalik, IV, Henry A.; Coates, Geoffrey W.

    2015-06-11

    Highly base-stable cationic moieties are a critical component of anion exchange membranes (AEMs) in alkaline fuel cells (AFCs); however, the commonly employed organic cations have limited alkaline stability. To address this problem, we synthesized and characterized the stability of a series of imidazolium cations in 1, 2, or 5 M KOH/CD 3OH at 80 °C, systematically evaluating the impact of substitution on chemical stability. The substituent identity at each position of the imidazolium ring has a dramatic effect on the overall cation stability. In conclusion, we report imidazolium cations that have the highest alkaline stabilities reported to date, >99% cationmore » remaining after 30 days in 5 M KOH/CD 3OH at 80 °C.« less

  10. Cation Selectivity in Biological Cation Channels Using Experimental Structural Information and Statistical Mechanical Simulation.

    PubMed

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

    2015-01-01

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

  11. Cation Selectivity in Biological Cation Channels Using Experimental Structural Information and Statistical Mechanical Simulation

    PubMed Central

    Finnerty, Justin John

    2015-01-01

    Cation selective channels constitute the gate for ion currents through the cell membrane. Here we present an improved statistical mechanical model based on atomistic structural information, cation hydration state and without tuned parameters that reproduces the selectivity of biological Na+ and Ca2+ ion channels. The importance of the inclusion of step-wise cation hydration in these results confirms the essential role partial dehydration plays in the bacterial Na+ channels. The model, proven reliable against experimental data, could be straightforwardly used for designing Na+ and Ca2+ selective nanopores. PMID:26460827

  12. Distribution of Cd and other cations between the stroma and thylakoids: a quantitative approach to the search for Cd targets in chloroplasts.

    PubMed

    Lysenko, Eugene A; Klaus, Alexander A; Kartashov, Alexander V; Kusnetsov, Victor V

    2018-06-21

    Plant growth and photosynthetic activity are usually inhibited due to the overall action of Cd on a whole organism, though few cadmium cations can invade chloroplasts in vivo. We found that in vivo, the major portion of Cd in barley chloroplasts is located in the thylakoids (80%), and the minor portion is in the stroma (20%). Therefore, the electron-transport chain in the thylakoids would be the likely target for direct Cd action in vivo. In vitro, we found the distribution of Cd to be shifted to the stroma (40-60%). In barley chloroplasts, the major portions of Mg, Fe, Mn, and Cu were found to be located in the thylakoids, and most Ca, Zn, and K in the stroma. This finding was true for both control and Cu- or Fe-treated plants. Treatment with Cd affected the contents of all cations, and the largest portions of Ca and Zn were in the thylakoids. Alterations of the K and Mn contents were caused by Cd, Cu, or Fe treatment; the levels of other cations in chloroplasts were changed specifically by Cd treatment. The quantity of Cd in chloroplasts was small in comparison to that of Mg, Ca, and Fe. In thylakoids, the amount of Cd was similar to that of Cu and comparable to the levels of Zn and Mn. Accordingly, the possible targets for direct Cd action in thylakoids are the Mn cluster, plastocyanin, carbonic anhydrase, or FtsH protease. The quantity of Cd in thylakoids is sufficient to replace a cation nearly completely at one of these sites or partially (20-30%) at many of these sites.

  13. ADSORPTION METHOD FOR SEPARATING METAL CATIONS

    DOEpatents

    Khym, J.X.

    1959-03-10

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

  14. Variation in whole DNA methylation in red maple (Acer rubrum) populations from a mining region: association with metal contamination and cation exchange capacity (CEC) in podzolic soils.

    PubMed

    Kalubi, K N; Mehes-Smith, M; Spiers, G; Omri, A

    2017-04-01

    Although a number of publications have provided convincing evidence that abiotic stresses such as drought and high salinity are involved in DNA methylation reports on the effects of metal contamination, pH, and cation exchange on DNA modifications are limited. The main objective of the present study is to determine the relationship between metal contamination and Cation exchange capacity (CEC) on whole DNA modifications. Metal analysis confirms that nickel and copper are the main contaminants in sampled sites within the Greater Sudbury Region (Ontario, Canada) and liming has increased soil pH significantly even after 30 years following dolomitic limestone applications. The estimated CEC values varied significantly among sites, ranging between 1.8 and 10.5 cmol(+) kg -1 , with a strong relationship being observed between CEC and pH (r = 0.96**). Cation exchange capacity, significantly lower in highly metal contaminated sites compared to both reference and less contaminated sites, was higher in the higher organic matter limed compared to unlimed sites. There was a significant variation in the level of cytosine methylation among the metal-contaminated sites. Significant and strong negative correlations between [5mdC]/[dG] and bioavailable nickel (r = -0.71**) or copper (r = -0.72**) contents were observed. The analysis of genomic DNA for adenine methylation in this study showed a very low level of [6N-mdA]/dT] in Acer rubrum plants analyzed ranging from 0 to 0.08%. Significant and very strong positive correlation was observed between [6N-mdA]/dT] and soil bioavailable nickel (r = 0.78**) and copper (r = 0.88**) content. This suggests that the increased bioavailable metal levels associated with contamination by nickel and copper particulates are associated with cytosine and adenine methylation.

  15. Structure and dynamics of cationic membrane peptides and proteins: Insights from solid-state NMR

    PubMed Central

    Hong, Mei; Su, Yongchao

    2011-01-01

    Many membrane peptides and protein domains contain functionally important cationic Arg and Lys residues, whose insertion into the hydrophobic interior of the lipid bilayer encounters significant energy barriers. To understand how these cationic molecules overcome the free energy barrier to insert into the lipid membrane, we have used solid-state NMR spectroscopy to determine the membrane-bound topology of these peptides. A versatile array of solid-state NMR experiments now readily yields the conformation, dynamics, orientation, depth of insertion, and site-specific protein–lipid interactions of these molecules. We summarize key findings of several Arg-rich membrane peptides, including β-sheet antimicrobial peptides, unstructured cell-penetrating peptides, and the voltage-sensing helix of voltage-gated potassium channels. Our results indicate the central role of guanidinium-phosphate and guanidinium-water interactions in dictating the structural topology of these cationic molecules in the lipid membrane, which in turn account for the mechanisms of this functionally diverse class of membrane peptides. PMID:21344534

  16. High-pressure behavior of A 2 B 2 O 7 pyrochlore (A=Eu, Dy; B=Ti, Zr)

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

    Rittman, Dylan R.; Turner, Katlyn M.; Park, Sulgiye

    2017-01-24

    In situ high-pressure X-ray diffraction and Raman spectroscopy were used to determine the influence of composition on the high-pressure behavior of A 2B 2O 7 pyrochlore (A = Eu, Dy; B = Ti, Zr) up to ~50 GPa. Based on X-ray diffraction results, all compositions transformed to the high-pressure cotunnite structure. The B-site cation species had a larger effect on the transition pressure than the A-site cation species, with the onset of the phase transformation occurring at ~41 GPa for B = Ti and ~16 GPa B = Zr. But, the A-site cation affected the kinetics of the phase transformation,more » with the transformation for compositions with the smaller ionic radii, i.e., A = Dy, proceeding faster than those with a larger ionic radii, i.e., A = Eu. Our results were consistent with previous work in which the radius-ratio of the A- and B-site cations determined the energetics of disordering, and compositions with more similarly sized A- and B-site cations had a lower defect formation energy. Raman spectra revealed differences in the degree of short-range order of the different compositions. Due to the large phase fraction of cotunnite at high pressure for B = Zr compositions, Raman modes for cotunnite could be observed, with more modes recorded for A = Eu than A = Dy. These additional modes are attributed to increased short-to-medium range ordering in the initially pyrochlore structured Eu 2Zr 2O 7 as compared with the initially defect-fluorite structured Dy 2Zr 2O 7.« less

  17. Sorption of chlorophenols on microporous minerals: mechanism and influence of metal cations, solution pH, and humic acid.

    PubMed

    Yang, Hui; Hu, Yuanan; Cheng, Hefa

    2016-10-01

    Sorption of 2-chlorophenol (2-CP), 2,4-dichlorophenol (2,4-DCP), and 2,4,6-trichlorophenol (2,4,6-TCP) on a range of dealuminated zeolites were investigated to understand the mechanism of their sorption on microporous minerals, while the influence of common metal cations, solution pH, and humic acid was also studied. Sorption of chlorophenols was found to increase with the hydrophobicity of the sorbates and that of the microporous minerals, indicating the important role of hydrophobic interactions, while sorption was also stronger in the micropores of narrower sizes because of greater enhancement of the dispersion interactions. The presence of metal cations could enhance chlorophenol sorption due to the additional electrostatic attraction between metal cations exchanged into the mineral micropores and the chlorophenolates, and this effect was apparent on the mineral sorbent with a high density of surface cations (2.62 sites/nm(2)) in its micropores. Under circum-neutral or acidic conditions, neutral chlorophenol molecules adsorbed into the hydrophobic micropores through displacing the "loosely bound" water molecules, while their sorption was negligible under moderately alkaline conditions due to electrostatic repulsion between the negatively charged zeolite framework and anionic chlorophenolates. The influence of humic acid on sorption of chlorophenols on dealuminated Y zeolites suggests that its molecules did not block the micropores but created a secondary sorption sites by forming a "coating layer" on the external surface of the zeolites. These mechanistic insights could help better understand the interactions of ionizable chlorophenols and metal cations in mineral micropores and guide the selection and design of reusable microporous mineral sorbents for sorptive removal of chlorophenols from aqueous stream.

  18. Computational study for the circular redox reaction of N2O with CO catalyzed by fullerometallic cations C60Fe+ and C70Fe.

    PubMed

    Anafcheh, Maryam; Naderi, Fereshteh; Khodadadi, Zahra; Ektefa, Fatemeh; Ghafouri, Reza; Zahedi, Mansour

    2017-03-01

    We applied density functional calculations to study the circular redox reaction mechanism of N 2 O with CO catalyzed by fullerometallic cations C 60 Fe + and C 70 Fe + . The on-top sites of six-membered rings (η 6 ) of fullerene cages are the most preferred binding sites for Fe + cation, and the hexagon to pentagon migration of Fe + is unlikely under ambient thermodynamic conditions. The initial ion/molecule reaction, N 2 O rearrangement and N 2 abstraction on the considered fullerometallic cations are easier than those on the bare Fe + cation in the gas phase. Generally, our results indicate that fullerometallic ions, C 60 Fe + and C 70 Fe + , are more favorable substrates for redox reaction of N 2 O with CO in comparison to the other previously studied carbon nanostructures such as graphene and nanotubes. Copyright © 2016 Elsevier Inc. All rights reserved.

  19. Linking trace element variations with macronutrients and major cations in marine mussels Mytilus edulis and Perna viridis.

    PubMed

    Liu, Fengjie; Wang, Wen-Xiong

    2015-09-01

    Marine mussels have long been used as biomonitors of contamination of trace elements, but little is known about whether variation in tissue trace elements is significantly associated with those of macronutrients and major cations. The authors examined the variability of macronutrients and major cations and their potential relationships with bioaccumulation of trace elements. The authors analyzed the concentrations of macronutrients (C, N, P, S), major cations (Na, Mg, K, Ca), and trace elements (Al, V, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Cd, Ba, Pb) in the whole soft tissues of marine mussels Mytilus edulis and Perna viridis collected globally from 21 sites. The results showed that 12% to 84% of the variances in the trace elements was associated with major cations, and the tissue concentration of major cations such as Na and Mg in mussels was a good proxy for ambient seawater concentrations of the major cations. Specifically, bioaccumulation of most of the trace elements was significantly associated with major cations, and the relationships of major cations with trace cations and trace oxyanions were totally opposite. Furthermore, 14% to 69% of the variances in the trace elements were significantly associated with macronutrients. Notably, more than half of the variance in the tissue concentrations of As, Cd, V, Ba, and Pb was explained by the variance in macronutrients in one or both species. Because the tissue macronutrient concentrations were strongly associated with animal growth and reproduction, the observed coupling relationships indicated that these biological processes strongly influenced the bioaccumulation of some trace elements. The present study indicated that simultaneous quantification of macronutrients and major cations with trace elements can improve the interpretation of biomonitoring data. © 2015 SETAC.

  20. Cationized Carbohydrate Gas-Phase Fragmentation Chemistry

    NASA Astrophysics Data System (ADS)

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

    2017-04-01

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

  1. Fluorescent Protein-Based Ca2+ Sensor Reveals Global, Divalent Cation-Dependent Conformational Changes in Cardiac Troponin C.

    PubMed

    Badr, Myriam A; Pinto, Jose R; Davidson, Michael W; Chase, P Bryant

    2016-01-01

    Cardiac troponin C (cTnC) is a key effector in cardiac muscle excitation-contraction coupling as the Ca2+ sensing subunit responsible for controlling contraction. In this study, we generated several FRET sensors for divalent cations based on cTnC flanked by a donor fluorescent protein (CFP) and an acceptor fluorescent protein (YFP). The sensors report Ca2+ and Mg2+ binding, and relay global structural information about the structural relationship between cTnC's N- and C-domains. The sensors were first characterized using end point titrations to decipher the response to Ca2+ binding in the presence or absence of Mg2+. The sensor that exhibited the largest responses in end point titrations, CTV-TnC, (Cerulean, TnC, and Venus) was characterized more extensively. Most of the divalent cation-dependent FRET signal originates from the high affinity C-terminal EF hands. CTV-TnC reconstitutes into skinned fiber preparations indicating proper assembly of troponin complex, with only ~0.2 pCa unit rightward shift of Ca2+-sensitive force development compared to WT-cTnC. Affinity of CTV-TnC for divalent cations is in agreement with known values for WT-cTnC. Analytical ultracentrifugation indicates that CTV-TnC undergoes compaction as divalent cations bind. C-terminal sites induce ion-specific (Ca2+ versus Mg2+) conformational changes in cTnC. Our data also provide support for the presence of additional, non-EF-hand sites on cTnC for Mg2+ binding. In conclusion, we successfully generated a novel FRET-Ca2+ sensor based on full length cTnC with a variety of cellular applications. Our sensor reveals global structural information about cTnC upon divalent cation binding.

  2. Electron-impact excitation of diatomic hydride cations II: OH+ and SH+

    NASA Astrophysics Data System (ADS)

    Hamilton, James R.; Faure, Alexandre; Tennyson, Jonathan

    2018-05-01

    R-matrix calculations combined with the adiabatic-nuclei-rotation and Coulomb-Born approximations are used to compute electron-impact rotational rate coefficients for two open-shell diatomic cations of astrophysical interest: the hydoxyl and sulphanyl ions, OH+ and SH+. Hyperfine resolved rate coefficients are deduced using the infinite-order-sudden approximation. The propensity rule ΔF = Δj = ΔN = ±1 is observed, as is expected for cations with a large dipole moment. A model for OH+ excitation in the Orion Bar photon-dominated region is presented which nicely reproduces Herschel observations for an electron fraction xe = 10-4 and an OH+ column density of 3 × 1013 cm-2. Electron-impact electronic excitation cross-sections and rate coefficients for the ions are also presented.

  3. Electronic spectra of astrophysically interesting cations

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

    Maier, John P., E-mail: j.p.maier@unibas.ch; Rice, Corey A., E-mail: j.p.maier@unibas.ch; Mazzotti, Fabio J., E-mail: j.p.maier@unibas.ch

    2015-01-22

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

  4. The role of monovalent cations in the ATPase reaction of DNA gyrase.

    PubMed

    Hearnshaw, Stephen James; Chung, Terence Tsz-Hong; Stevenson, Clare Elizabeth Mary; Maxwell, Anthony; Lawson, David Mark

    2015-04-01

    Four new crystal structures of the ATPase domain of the GyrB subunit of Escherichia coli DNA gyrase have been determined. One of these, solved in the presence of K(+), is the highest resolution structure reported so far for this domain and, in conjunction with the three other structures, reveals new insights into the function of this domain. Evidence is provided for the existence of two monovalent cation-binding sites: site 1, which preferentially binds a K(+) ion that interacts directly with the α-phosphate of ATP, and site 2, which preferentially binds an Na(+) ion and the functional significance of which is not clear. The crystallographic data are corroborated by ATPase data, and the structures are compared with those of homologues to investigate the broader conservation of these sites.

  5. The role of monovalent cations in the ATPase reaction of DNA gyrase

    PubMed Central

    Hearnshaw, Stephen James; Chung, Terence Tsz-Hong; Stevenson, Clare Elizabeth Mary; Maxwell, Anthony; Lawson, David Mark

    2015-01-01

    Four new crystal structures of the ATPase domain of the GyrB subunit of Escherichia coli DNA gyrase have been determined. One of these, solved in the presence of K+, is the highest resolution structure reported so far for this domain and, in conjunction with the three other structures, reveals new insights into the function of this domain. Evidence is provided for the existence of two monovalent cation-binding sites: site 1, which preferentially binds a K+ ion that interacts directly with the α-phosphate of ATP, and site 2, which preferentially binds an Na+ ion and the functional significance of which is not clear. The crystallographic data are corroborated by ATPase data, and the structures are compared with those of homologues to investigate the broader conservation of these sites. PMID:25849408

  6. Adsorption Behavior of Rare Earth Metal Cations in the Interlayer Space of γ-ZrP.

    PubMed

    Takei, Takahiro; Iidzuka, Kiyoaki; Miura, Akira; Yanagida, Sayaka; Kumada, Nobuhiro; Magome, Eisuke; Moriyoshi, Chikako; Kuroiwa, Yoshihiro

    2016-10-04

    Adsorption competencies of rare earth metal cations in γ-zirconium phosphate were examined by ICP, synchrotron X-ray diffraction (SXRD), and ab initio simulation. The adsorption amounts are around 0.06-0.10 per zirconium phosphate. From the SXRD patterns of the adsorbed samples, the basal spacing estimated by c sin β increased linearly with an increasing ionic radius of rare earth metal cation, though a and b lattice constants show no change. These SXRD patterns can be classified into four groups that have different super lattices. The four superlattices have multiplicities of x131, x241, and x221 for the xabc axis, and the location of the rare earth metal cation in the original unit cell changes depending on the superlattice cell. In the x131 superlattice, Yb and Er occupied the site near the zirconium phosphate layer, though La and Ce in the x221 superlattice remained in the center position between the phosphate sheet. For the ab initio simulation of γ-ZrP with the typical rare earth metal cations (Tb, Eu, Dy, and La), the results of simulation show a similar tendency of the position estimated by SXRD refinements.

  7. Cation vacancies in ferroelectric PbTiO3 and Pb(Zr,Ti)O3 : A positron annihilation lifetime spectroscopy study

    NASA Astrophysics Data System (ADS)

    Keeble, D. J.; Singh, S.; Mackie, R. A.; Morozov, M.; McGuire, S.; Damjanovic, D.

    2007-10-01

    Positron annihilation lifetime spectroscopy measurements identify A - and B -site cation vacancies in ferroelectric perovskite oxides (ABO3) . Crystal PbTiO3 and ceramic lead zirconium titanate (PZT) were studied and gave consistent values for the lifetime resulting from positron localization at lead vacancies VPb . Positron trapping to B -site vacancies was inferred in PZT. Temperature dependent studies showed that the defect specific trapping rate was higher for VB compared to VPb , consistent with the larger negative charge. Doping PZT with Fe increased the fraction positron trapping to VB compared to VPb -type defects.

  8. A simple model for metal cation-phosphate interactions in nucleic acids in the gas phase: alkali metal cations and trimethyl phosphate.

    PubMed

    Ruan, Chunhai; Huang, Hai; Rodgers, M T

    2008-02-01

    Threshold collision-induced dissociation techniques are employed to determine the bond dissociation energies (BDEs) of complexes of alkali metal cations to trimethyl phosphate, TMP. Endothermic loss of the intact TMP ligand is the only dissociation pathway observed for all complexes. Theoretical calculations at the B3LYP/6-31G* level of theory are used to determine the structures, vibrational frequencies, and rotational constants of neutral TMP and the M+(TMP) complexes. Theoretical BDEs are determined from single point energy calculations at the B3LYP/6-311+G(2d,2p) level using the B3LYP/6-31G* optimized geometries. The agreement between theory and experiment is reasonably good for all complexes except Li+(TMP). The absolute M+-(TMP) BDEs are found to decrease monotonically as the size of the alkali metal cation increases. No activated dissociation was observed for alkali metal cation binding to TMP. The binding of alkali metal cations to TMP is compared with that to acetone and methanol.

  9. Evidence for Cation-Controlled Excited-State Localization in a Ruthenium Polypyridyl Compound.

    PubMed

    Beauvilliers, Evan E; Meyer, Gerald J

    2016-08-01

    The visible absorption and photoluminescence (PL) properties of the four neutral ruthenium diimine compounds [Ru(bpy)2(dcb)] (B2B), [Ru(dtb)2(dcb)] (D2B), [Ru(bpy)2(dcbq)] (B2Q), and [Ru(dtb)2(dcbq)] (D2Q), where bpy is 2,2'-bipyridine, dcb is 4,4'-(CO2(-))2-bpy, dtb is 4,4'-(tert-butyl)2-bpy, and dcbq is 4,4'-(CO2(-))2-2,2'-biquinoline, are reported in the presence of Lewis acidic cations present in fluid solutions at room temperature. In methanol solutions, the measured spectra were insensitive to the presence of these cations, while in acetonitrile a significant red shift in the PL spectra (≤1400 cm(-1)) was observed consistent with stabilization of the metal-to-ligand charge transfer (MLCT) excited state through Lewis acid-base adduct formation. No significant spectral changes were observed in control experiments with the tetrabutylammonium cation. Titration data with Li(+), Na(+), Mg(2+), Ca(2+), Zn(2+), Al(3+), Y(3+), and La(3+) showed that the extent of stabilization saturated at high cation concentration with magnitudes that scaled roughly with the cation charge-to-size ratio. The visible absorption spectra of D2Q was particularly informative due to the presence of two well-resolved MLCT absorption bands: (1) Ru → bpy, λmax ≈ 450 nm; and (2) Ru → dcbq, λmax ≈ 540 nm. The higher-energy band blue-shifted and the lower-energy band red-shifted upon cation addition. The PL intensity and lifetime of the excited state of B2B first increased with cation addition without significant shifts in the measured spectra, behavior attributed to a cation-induced change in the localization of the emissive excited state from bpy to dcb. The importance of excited-state localization and stabilization for solar energy conversion is discussed.

  10. Inferred cation reordering in natural titanomagnetites with implications for Curie temperature and other magnetic properties (Invited)

    NASA Astrophysics Data System (ADS)

    Bowles, J. A.; Jackson, M. J.; Berquo, T. S.; Solheid, P.; Lappe, S. L.; Gee, J. S.

    2013-12-01

    We will present the results of recent work demonstrating that some natural titanomagnetites of common composition undergo cation reordering on laboratory timescales and at temperatures just above or below the Curie temperature (TC). This cation reordering produces changes in Curie temperature that have important implications for paleomagnetic studies and our understanding of remanence acquisition when TC is a function of prior thermal history. The bulk composition of the titanomagnetites (Fe3-xTixO4) varies between approximately 0.2 < x < 0.4, with moderate degrees of Mg and Al substitution. This composition is extremely common in rocks of andesitic, dacitic, and rhyolitic composition, as well as in some basalts. Samples were annealed for 10-1 to 103 hr at 350-425°C, producing large and reversible changes in TC (up to 150°C) that are roughly linear with log(anneal time). By ruling out oxidation/reduction and compositional unmixing, we interpret the variations in TC as arising from the re-distribution of ferric and ferrous iron cations between the octahedral and tetrahedral sites. Mössbauer spectroscopy supports this interpretation. Unlike pure titanomagnetite, the kinetics of the reordering process in these Mg- and Al-substituted natural titanomagnetites are apparently slow enough that intermediate degrees of ordering can be preserved by rapid quenching. The magnitude of the variation in TC produced by annealing at moderate temperatures correlates most strongly with Mg and Ti content and weakly with Al content. While strong variations are observed in TC, no detectible variation is found in saturation magnetization, and blocking temperature variations only weakly correlate with TC variation.

  11. Crystal structure of channelrhodopsin, a light-gated cation channel – all cations lead through the monomer –

    PubMed Central

    Kato, Hideaki E.; Nureki, Osamu

    2013-01-01

    Channelrhodopsin (ChR) is a light-gated cation channel derived from green algae. Since the inward flow of cations triggers the neuron firing, neurons expressing ChRs can be optically controlled even within freely moving mammals. Although ChR has been broadly applied to neuro-science research, little is known about its molecular mechanisms. We determined the crystal structure of chimeric ChR at 2.3 Å resolution and revealed its molecular architecture. The integration of structural, electrophysio-logical, and computational analyses provided insight into the molecular basis for the channel function of ChR, and paved the way for the principled design of ChR variants with novel properties. PMID:27493541

  12. Crystal structure refinement and Mössbauer spectroscopy of an ordered, triclinic clinochlore

    USGS Publications Warehouse

    Smyth, Joseph R.; Dyar, M. Darby; May, Howard M.; Bricker, Owen P.; Acker, James G.

    1997-01-01

    The crystal structure of a natural, ordered IIb-4 triclinic clinochlore has been refined in space group C1¯ from 4282 unique X-ray intensity measurements of which 3833 are greater than 3 times the statistical counting error (3σ). Unit cell parameters are a = 5.3262(6) Å; b = 9.226(1) Å; c = 14.334(3) Å; α = 90.56(2)°; β = 97.47(2)°; and γ = 89.979(9)°, which represents the greatest deviation from monoclinic symmetry yet recorded for a triclinic chlorite. The final weighted R is 0.059 for reflections with I > 3σ and 0.064 for all reflections. The chemical formula is (Mg0.966Fe0.034)M1(Mg0.962Fe0.038)M22(Si2.96Al1.04)O10 (OH)2(Mg0.996Fe0.004)M32(Al0.841FeIII0.102Cr0.004Ti0.004)M4(OH)6, which is consistent with electron microprobe (EMP), wet chemical analyses, Mössbauer spectroscopy and X-ray structure refinement. The high degree of ordering of the divalent versus trivalent octahedral cations in the interlayer is noteworthy, with FeIII and Al in M4 and virtually no Fe in M3. In the 2:1 layer, M1 and M2 each contain similar amounts of Fe. The 2 tetrahedral sites have nearly identical mean oxygen distances and volumes, and thus show no evidence of long-range cation ordering.

  13. The effect of alkaline cations on the Intercalation of Carbon Dioxide in Sepiolite Minerals: a Molecular Dynamics Investigation.

    NASA Astrophysics Data System (ADS)

    Tavanti, Francesco; Muniz-Miranda, Francesco; Pedone, Alfonso

    2018-03-01

    The ability of the sepiolite mineral to intercalate CO2 molecules inside its channels in the presence of different alkaline cations (K+, Na+ and Li+) has been studied by classical Molecular Dynamics simulations. Starting from an alkaline-free sepiolite crystalline model we built three models with stoichiometry Mg320Si440Al40O1200(OH)160X+40•480H2O. On these models, we gradually replaced the water molecules present in the channels with carbon dioxide and determined the energy of this exchange reaction as well as the structural organization and dynamics of carbon dioxide in the channels. The adsorption energy shows that the Li-containing sepiolite mineral retains more carbon dioxide with respect to those with sodium and potassium cations in the channels. Moreover, the ordered patterns of CO2 molecules observed in the alkaline-free sepiolite mineral are in part destabilized by the presence of cations decreasing the adsorption capacity of this clay mineral.

  14. 77 FR 52322 - McClellan Air Force Base Superfund Site Proposed Notice of Administrative Order on Consent

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-08-29

    ... ENVIRONMENTAL PROTECTION AGENCY [FRL-9723-5] McClellan Air Force Base Superfund Site Proposed Notice of Administrative Order on Consent AGENCY: Environmental Protection Agency (EPA). ACTION: Notice... consent concerning portions of the McClellan Air Force Base Superfund Site (``Site'') in McClellan...

  15. On the different roles of anions and cations in the solvation of enzymes in ionic liquids.

    PubMed

    Klähn, Marco; Lim, Geraldine S; Seduraman, Abirami; Wu, Ping

    2011-01-28

    The solvation of the enzyme Candida antarctica lipase B (CAL-B) was studied in eight different ionic liquids (ILs). The influence of enzyme-ion interactions on the solvation of CAL-B and the structure of the enzyme-IL interface are analyzed. CAL-B and ILs are described with molecular dynamics (MD) simulations in combination with an atomistic empirical force field. The considered cations are based on imidazolium or guanidinium that are paired with nitrate, tetrafluoroborate or hexafluorophosphate anions. The interactions of CAL-B with ILs are dominated by Coulomb interactions with anions, while the second largest contribution stems from van der Waals interactions with cations. The enzyme-ion interaction strength is determined by the ion size and the magnitude of the ion surface charge. The solvation of CAL-B in ILs is unfavorable compared to water because of large formation energies for the CAL-B solute cages in ILs. The internal energy in the IL and of CAL-B increases linearly with the enzyme-ion interaction strength. The average electrostatic potential on the surface of CAL-B is larger in ILs than in water, due to a weaker screening of charged enzyme residues. Ion densities increased moderately in the vicinity of charged residues and decreased close to non-polar residues. An aggregation of long alkyl chains close to non-polar regions and the active site entrance of CAL-B are observed in one IL that involved long non-polar decyl groups. In ILs that contain 1-butyl-3-methylimidazolium cations, the diffusion of one or two cations into the active site of CAL-B occurs during MD simulations. This suggests a possible obstruction of the active site in these ILs. Overall, the results indicate that small ions lead to a stronger electrostatic screening within the solvent and stronger interactions with the enzyme. Also a large ion surface charge, when more hydrophilic ions are used, increases enzyme-IL interactions. An increase of these interactions destabilizes the enzyme

  16. Two cation exchange models for direct and inverse modelling of solution major cation composition in equilibrium with illite surfaces

    NASA Astrophysics Data System (ADS)

    Tournassat, Christophe; Gailhanou, Hélène; Crouzet, Catherine; Braibant, Gilles; Gautier, Anne; Lassin, Arnault; Blanc, Philippe; Gaucher, Eric C.

    2007-03-01

    Na/K, Na/Ca and Na/Mg exchange isotherms were performed on the fine fraction (<2 μm) of Imt-2 illite samples at a total normality of about 0.005 mol/L in anionic chloride medium. The derived selectivity coefficients for Na/K, Na/Ca and Na/Mg were found to vary as a function of the exchanger composition and compared well with the data collected in the literature for similar experimental conditions. Two models were built to reproduce the data: the first was a multi(2)-site model with constant Gaines and Thomas selectivity coefficients; the second was a one-site model taking into account surface species activity coefficients. The results of the models were in rather good agreement with both our data and literature data. The multi-site model proved to be efficient in predicting the exchanger composition as a function of the Na/Ca/Mg/K concentrations in solution, whereas the one-site model proved to be a better approach to derive the Na/Ca/Mg/K concentrations in solution based on the knowledge of the exchanger composition and the total normality of the solution. The interest of this approach is illustrated by the need for major cation solute concentration predictions in compacted clay for the characterization of nuclear deep disposal host rock repositories.

  17. IR and TPD studies of the interaction of alkenes with Cu + sites in CuNaY and CuNaX zeolites of various Cu content. The heterogeneity of Cu + sites

    NASA Astrophysics Data System (ADS)

    Datka, J.; Kukulska-Zajaç, E.; Kozyra, P.

    2006-08-01

    Cu + ions in zeolites activate organic molecules containing π electrons by π back donation, which results in a distinct weakening of multiple bonds. In this study, we followed the activation of alkenes (ethene and propene) by Cu + ions in CuY and CuX zeolites of various Cu content. We also studied the strength of bonding of alkenes to Cu + ions. IR studies have shown that there are two kinds of Cu + sites of various electron donor properties. We suppose that they could be attributed to the presence of Cu + ions of various number of oxygen atoms surrounding the cation. IR studies have shown that Cu ions introduced into Y and X zeolites in the first-order (at low Cu content) form Cu + ions of stronger electron donor properties (i.e. activate alkenes to larger extend) than Cu ions introduced in the next order (at higher Cu content). IR and TPD studies of alkenes desorption evidenced that Cu + ions of stronger electron donor properties bond alkenes stronger than less electron donor ones. It suggests that π back donation has more important contribution to the strength of bonding alkenes to cation than π donation.

  18. Super-high-affinity binding site for [3H]diazepam in the presence of Co2+, Ni2+, Cu2+, or Zn2+.

    PubMed

    Mizuno, S; Ogawa, N; Mori, A

    1982-12-01

    Chloride salts of Li+, Na+, K+, Mg2+, Ca2+, Cr3+, Mn2+, Fe2+, and Fe3+ had no effect on [3H]diazepam binding. Chloride salts of Co2+, Ni2+, Cu2+, and Zn2+ increased [3H]diazepam binding by 34 to 68% in a concentration-dependent fashion. Since these divalent cations potentiated the GABA-enhanced [3H]diazepam binding and the effect of each divalent cation was nearly additive with GABA, these cations probably act at a site different from the GABA recognition site in the benzodiazepine-receptor complex. Scatchard plots of [3H]diazepam binding without an effective divalent cation showed a single class of binding, with a Kd value of 5.3 nM. In the presence of 1 mM Co2+, Ni2+, Cu2+, or Zn2+, two distinct binding sites were evident with apparent Kd values of 1.0 nM and 5.7 nM. The higher-affinity binding was not detected in the absence of an effective divalent cation and is probably a novel, super-high-affinity binding site.

  19. Spectroscopy and computational studies on the interaction of octyl, dodecyl, and hexadecyl derivatives of anionic and cationic surfactants with adenosine deaminase.

    PubMed

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

    2016-07-01

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

  20. Plant rhamnogalacturonan II complexation of heavy metal cations

    DOEpatents

    O`Neill, M.A.; Pellerin, P.J.M.; Warrenfeltz, D.; Vidal, S.; Darvill, A.G.; Albersheim, P.

    1999-03-02

    The present invention provides rhamnogalacturonan-II (RG-II) and relates to its ability to complex specific multivalent heavy metal cations. In the presence of boric acid, RG-II monomers form dimers that are cross-linked by a borate ester. The yield of such borate ester cross-linked dimers of RG-II is enhanced in the presence of specific heavy metal cations. The present invention further relates to the utility of RG-II in assays for the detection of specific heavy metal contamination; as a reagent useful in the removal of specific heavy metal cations contaminating foods and liquids, for example, fish, wines, etc.; as a pharmaceutical composition useful as an antidote in specific heavy metal cation poisoning; as a treatment for the detoxification of specific heavy metal cations from blood and/or tissues; and in a method of remediation of waters and soils contaminated with specific heavy metal cations. 15 figs.

  1. Plant rhamnogalacturonan II complexation of heavy metal cations

    DOEpatents

    O'Neill, Malcolm A.; Pellerin, Patrice J. M.; Warrenfeltz, Dennis; Vidal, Stephane; Darvill, Alan G.; Albersheim, Peter

    1999-01-01

    The present invention provides rhamnogalacturonan-II (RG-II) and relates to its ability to complex specific multivalent heavy metal cations. In the presence of boric acid, RG-II monomers form dimers that are cross-linked by a borate ester. The yield of such borate ester cross-linked dimers of RG-II is enhanced in the presence of specific heavy metal cations. The present invention further relates to the utility of RG-II in assays for the detection of specific heavy metal contamination; as a reagent useful in the removal of specific heavy metal cations contaminating foods and liquids, for example, fish, wines, etc.; as a pharmaceutical composition useful as an antidote in specific heavy metal cation poisoning; as a treatment for the detoxification of specific heavy metal cations from blood and/or tissues; and in a method of remediation of waters and soils contaminated with specific heavy metal cations.

  2. Single-Molecule Kinetics Reveal Cation-Promoted DNA Duplex Formation Through Ordering of Single-Stranded Helices

    PubMed Central

    Dupuis, Nicholas F.; Holmstrom, Erik D.; Nesbitt, David J.

    2013-01-01

    In this work, the kinetics of short, fully complementary oligonucleotides are investigated at the single-molecule level. Constructs 6–9 bp in length exhibit single exponential kinetics over 2 orders of magnitude time for both forward (kon, association) and reverse (koff, dissociation) processes. Bimolecular rate constants for association are weakly sensitive to the number of basepairs in the duplex, with a 2.5-fold increase between 9 bp (k′on = 2.1(1) × 106 M−1 s−1) and 6 bp (k′on = 5.0(1) × 106 M−1 s−1) sequences. In sharp contrast, however, dissociation rate constants prove to be exponentially sensitive to sequence length, varying by nearly 600-fold over the same 9 bp (koff = 0.024 s−1) to 6 bp (koff = 14 s−1) range. The 8 bp sequence is explored in more detail, and the NaCl dependence of kon and koff is measured. Interestingly, konincreases by >40-fold (kon = 0.10(1) s−1 to 4.0(4) s−1 between [NaCl] = 25 mM and 1 M), whereas in contrast, koffdecreases by fourfold (0.72(3) s−1 to 0.17(7) s−1) over the same range of conditions. Thus, the equilibrium constant (Keq) increases by ≈160, largely due to changes in the association rate, kon. Finally, temperature-dependent measurements reveal that increased [NaCl] reduces the overall exothermicity (ΔΔH° > 0) of duplex formation, albeit by an amount smaller than the reduction in entropic penalty (−TΔΔS° < 0). This reduced entropic cost is attributed to a cation-facilitated preordering of the two single-stranded species, which lowers the association free-energy barrier and in turn accelerates the rate of duplex formation. PMID:23931323

  3. 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.

  4. Former charcoal kiln sites where forest was cleared for cultivation: a case study of old biochar in cropland

    NASA Astrophysics Data System (ADS)

    Hardy, Brieuc; Dufey, Joseph E.; Cornelis, Jean-Thomas

    2014-05-01

    The use of biochar as a soil amendment is being increasingly investigated as a win-win solution for mitigating the anthropic CO2 emissions and improving soil fertility. However, data on the long term impact of chars on soil properties are scarce, although they are crucial for better understanding the implications of large scale application of highly persistent biochars to soil. In Wallonia (Belgium), old charcoal kilns are found in most of the area that was forested in the late 18th century. Since then, a non-negligible part of the forest has been cleared for cultivation. Today, old charcoal-making platforms can be seen on bare soils as circular or elliptic black spots due to charcoal enrichment. In order to assess the long-term (>200 years) effects of biochar on soil chemical properties, seventeen kiln sites were chosen in several cropland areas of Wallonia on loessic luvisols (14) and loamy cambisols (3). Composite samples were taken in the ploughing layer (0 - 25 cm) and the underlying horizon (35 - 50 cm) in and out the kiln sites. The pH, total carbon (C) and nitrogen (N) contents, oxidizable carbon (CW&B), available phosphorus (Pav), cation exchange capacity at pH 7 (CEC), exchangeable cations content (Ca++, Mg++, K+, Na+) and loss on ignition at 550°C (LI550) were measured. In order to assess the impact of cultivation on charcoal aging, we also sampled four kiln sites on loessic luvisols under forest. Here, we show that charcoal, diluted laterally by successive tillage, acts as a carbon surplus in the topsoil layer of the black spots. The charcoal-enriched horizon is characterized by higher CEC, C/N and C/LI550 ratio compared to the reference soil. Cultivation of former forest soils accelerates charcoal aging, likely due to a combined effect of mechanical (tillage splits charcoal fragments in smaller pieces and increases soil aeration) and biological actions (promoted by improved trophic conditions due to application of amendments and fertilizers over many

  5. Penetrating cation/fatty acid anion pair as a mitochondria-targeted protonophore

    PubMed Central

    Severin, Fedor F.; Severina, Inna I.; Antonenko, Yury N.; Rokitskaya, Tatiana I.; Cherepanov, Dmitry A.; Mokhova, Elena N.; Vyssokikh, Mikhail Yu.; Pustovidko, Antonina V.; Markova, Olga V.; Yaguzhinsky, Lev S.; Korshunova, Galina A.; Sumbatyan, Nataliya V.; Skulachev, Maxim V.; Skulachev, Vladimir P.

    2010-01-01

    A unique phenomenon of mitochondria-targeted protonophores is described. It consists in a transmembrane H+-conducting fatty acid cycling mediated by penetrating cations such as 10-(6’-plastoquinonyl)decyltriphenylphosphonium (SkQ1) or dodecyltriphenylphosphonium (C12TPP). The phenomenon has been modeled by molecular dynamics and directly proved by experiments on bilayer planar phospholipid membrane, liposomes, isolated mitochondria, and yeast cells. In bilayer planar phospholipid membrane, the concerted action of penetrating cations and fatty acids is found to result in conversion of a pH gradient (ΔpH) to a membrane potential (Δψ) of the Nernstian value (about 60 mV Δψ at ΔpH = 1). A hydrophobic cation with localized charge (cetyltrimethylammonium) failed to substitute for hydrophobic cations with delocalized charge. In isolated mitochondria, SkQ1 and C12TPP, but not cetyltrimethylammonium, potentiated fatty acid-induced (i) uncoupling of respiration and phosphorylation, and (ii) inhibition of H2O2 formation. In intact yeast cells, C12TPP stimulated respiration regardless of the extracellular pH value, whereas a nontargeted protonophorous uncoupler (trifluoromethoxycarbonylcyanide phenylhydrazone) stimulated respiration at pH 5 but not at pH 3. Hydrophobic penetrating cations might be promising to treat obesity, senescence, and some kinds of cancer that require mitochondrial hyperpolarization. PMID:20080732

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

    PubMed

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

    2013-06-01

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

  7. Towards Extending Solar Cell Lifetimes: Addition of a Fluorous Cation to Triple Cation-Based Perovskite Films.

    PubMed

    Salado, Manuel; Fernández, M Asunción; Holgado, Juan P; Kazim, Samrana; Nazeeruddin, Mohammad Khaja; Dyson, Paul J; Ahmad, Shahzada

    2017-10-09

    Organohalide perovskites have emerged as highly promising replacements for thin-film solar cells. However, their poor stability under ambient conditions remains problematic, hindering commercial exploitation. The addition of a fluorous-functionalized imidazolium cation during the preparation of a highly stable cesium-based mixed perovskite material Cs 0.05 (MA 0.15 FA 0.85 ) 0.95 Pb(I 0.85 Br 0.15 ) 3 (MA=methylammonium; FA=formamidinium) has been shown to influence its stability. The resulting materials, which vary according to the amount of the fluorous-functionalized imidazolium cation present during fabrication, display a prolonged tolerance to atmospheric humidity (>100 days) along with power conversion efficiencies exceeding 16 %. This work provides a general route that can be implemented in a variety of perovskites and highlights a promising way to increase perovskite solar cell stability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Diffusion of cations in chromia layers grown on iron-base alloys

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

    Lobnig, R.E.; Hennesen, K.; Grabke, H.J.

    Diffusion of the cations Cr, Fe, Mn, and Ni in Cr{sub 2}O{sub 3} has been investigated at 1,173 K. The diffusion measurements were performed on chromia layers grown on the model alloys Fe-20Cr and Fe-20Cr-12Ni in order to consider effects of small amounts of dissolved alien cations in Cr{sub 2}O{sub 3}. The samples were diffusion annealed in H{sub 2}-H{sub 2}O at an oxygen partial pressure close to the Cr{sub 2}O{sub 3}/Cr equilibrium. For all tracers the lattice-diffusion coefficients are 3-5 orders of magnitude smaller than the grain-boundary diffusion coefficients. The lattice diffusivity of Mn is about two orders of magnitudemore » greater than the other lattice-diffusion coefficients, especially in Cr{sub 2}O{sub 3} grown on Fe-20Cr-12Ni. The values of the diffusion coefficients for Cr, Fe, and Ni are in the same range. Diffusion of the tracers in Cr{sub 2}O{sub 3} grown on different alloys did not show significant differences with the exception of Mn.« less

  9. Water soluble cations and the fluvial history of Mars

    NASA Technical Reports Server (NTRS)

    Silverman, M. P.; Munoz, E. F.

    1975-01-01

    The electrical conductivity and water soluble Na, K, Ca, and Mg of aqueous solutions of terrestrial soils and finely divided igneous and metamorphic rocks were determined. Soils from dry terrestrial basins with a history of water accumulation as well as soils from the topographic lows of valleys accumulated water soluble cations, particularly Na and Ca. These soils as a group can be distinguished from the rocks or a second group of soils (leached upland soils and soils from sites other than the topographic lows of valleys) by significant differences in their mean electrical conductivity and water-soluble Na + Ca content. Similar measurements on multiple samples from the surface of Mars, collected by an automated long-range roving vehicle along a highlands-to-basin transect at sites with morphological features resembling dry riverlike channels, are suggested to determine the fluvial history of the planet.

  10. Charge Shielding of PIP2 by Cations Regulates Enzyme Activity of Phospholipase C

    PubMed Central

    Seo, Jong Bae; Jung, Seung-Ryoung; Huang, Weigang; Zhang, Qisheng; Koh, Duk-Su

    2015-01-01

    Hydrolysis of phosphatidylinositol 4,5-bisphosphate (PIP2) of the plasma membrane by phospholipase C (PLC) generates two critical second messengers, inositol-1,4,5-trisphosphate and diacylglycerol. For the enzymatic reaction, PIP2 binds to positively charged amino acids in the pleckstrin homology domain of PLC. Here we tested the hypothesis that positively charged divalent and multivalent cations accumulate around the negatively charged PIP2, a process called electrostatic charge shielding, and therefore inhibit electrostatic PIP2-PLC interaction. This charge shielding of PIP2 was measured quantitatively with an in vitro enzyme assay using WH-15, a PIP2 analog, and various recombinant PLC proteins (β1, γ1, and δ1). Reduction of PLC activity by divalent cations, polyamines, and neomycin was well described by a theoretical model considering accumulation of cations around PIP2 via their electrostatic interaction and chemical binding. Finally, the charge shielding of PIP2 was also observed in live cells. Perfusion of the cations into cells via patch clamp pipette reduced PIP2 hydrolysis by PLC as triggered by M1 muscarinic receptors with a potency order of Mg2+ < spermine4+ < neomycin6+. Accumulation of divalent cations into cells through divalent-permeable TRPM7 channel had the same effect. Altogether our results suggest that Mg2+ and polyamines modulate the activity of PLCs by controlling the amount of free PIP2 available for the enzymes and that highly charged biomolecules can be inactivated by counterions electrostatically. PMID:26658739

  11. Charge Shielding of PIP2 by Cations Regulates Enzyme Activity of Phospholipase C.

    PubMed

    Seo, Jong Bae; Jung, Seung-Ryoung; Huang, Weigang; Zhang, Qisheng; Koh, Duk-Su

    2015-01-01

    Hydrolysis of phosphatidylinositol 4,5-bisphosphate (PIP2) of the plasma membrane by phospholipase C (PLC) generates two critical second messengers, inositol-1,4,5-trisphosphate and diacylglycerol. For the enzymatic reaction, PIP2 binds to positively charged amino acids in the pleckstrin homology domain of PLC. Here we tested the hypothesis that positively charged divalent and multivalent cations accumulate around the negatively charged PIP2, a process called electrostatic charge shielding, and therefore inhibit electrostatic PIP2-PLC interaction. This charge shielding of PIP2 was measured quantitatively with an in vitro enzyme assay using WH-15, a PIP2 analog, and various recombinant PLC proteins (β1, γ1, and δ1). Reduction of PLC activity by divalent cations, polyamines, and neomycin was well described by a theoretical model considering accumulation of cations around PIP2 via their electrostatic interaction and chemical binding. Finally, the charge shielding of PIP2 was also observed in live cells. Perfusion of the cations into cells via patch clamp pipette reduced PIP2 hydrolysis by PLC as triggered by M1 muscarinic receptors with a potency order of Mg2+ < spermine4+ < neomycin6+. Accumulation of divalent cations into cells through divalent-permeable TRPM7 channel had the same effect. Altogether our results suggest that Mg2+ and polyamines modulate the activity of PLCs by controlling the amount of free PIP2 available for the enzymes and that highly charged biomolecules can be inactivated by counterions electrostatically.

  12. Effect of counterions on the shape, hydration, and degree of order at the interface of cationic micelles: the triflate case.

    PubMed

    Lima, Filipe S; Cuccovia, Iolanda M; Horinek, Dominik; Amaral, Lia Q; Riske, Karin A; Schreier, Shirley; Salinas, Roberto K; Bastos, Erick L; Pires, Paulo A R; Bozelli, José Carlos; Favaro, Denize C; Rodrigues, Ana Clara B; Dias, Luís Gustavo; El Seoud, Omar A; Chaimovich, Hernan

    2013-04-02

    Specific ion effects in surfactant solutions affect the properties of micelles. Dodecyltrimethylammonium chloride (DTAC), bromide (DTAB), and methanesulfonate (DTAMs) micelles are typically spherical, but some organic anions can induce shape or phase transitions in DTA(+) micelles. Above a defined concentration, sodium triflate (NaTf) induces a phase separation in dodecyltrimethylammonium triflate (DTATf) micelles, a phenomenon rarely observed in cationic micelles. This unexpected behavior of the DTATf/NaTf system suggests that DTATf aggregates have unusual properties. The structural properties of DTATf micelles were analyzed by time-resolved fluorescence quenching, small-angle X-ray scattering, nuclear magnetic resonance, and electron paramagnetic resonance and compared with those of DTAC, DTAB, and DTAMs micelles. Compared to the other micelle types, the DTATf micelles had a higher average number of monomers per aggregate, an uncommon disk-like shape, smaller interfacial hydration, and restricted monomer chain mobility. Molecular dynamic simulations supported these observations. Even small water-soluble salts can profoundly affect micellar properties; our data demonstrate that the -CF3 group in Tf(-) was directly responsible for the observed shape changes by decreasing interfacial hydration and increasing the degree of order of the surfactant chains in the DTATf micelles.

  13. Crystal structures of K2[XSi5O12] (X = Fe2+, Co, Zn) and Rb2[XSi5O12] (X = Mn) leucites: comparison of monoclinic P21/c and Ia{\\overline 3}d polymorph structures and inverse relationship between tetrahedral cation (T = Si and X)-O bond distances and intertetrahedral T-O-T angles.

    PubMed

    Bell, Anthony M T; Henderson, C Michael B

    2018-06-01

    The leucite tectosilicate mineral analogues K 2 X 2+ Si 5 O 12 (X = Fe 2+ , Co, Zn) and Rb 2 X 2+ Si 5 O 12 (X = Mn) have been synthesized at elevated temperatures both dry at atmospheric pressure and at controlled water vapour pressure; for X = Co and Zn both dry and hydrothermally synthesized samples are available. Rietveld refinement of X-ray data for hydrothermal K 2 X 2+ Si 5 O 12 (X = Fe 2+ , Co, Zn) samples shows that they crystallize in the monoclinic space group P2 1 /c and have tetrahedral cations (Si and X) ordered onto distinct framework sites [cf. hydrothermal K 2 MgSi 5 O 12 ; Bell et al. (1994a), Acta Cryst. B50, 560-566]. Dry-synthesized K 2 X 2+ Si 5 O 12 (X = Co, Zn) and Rb 2 X 2+ Si 5 O 12 (X = Mn) samples crystallize in the cubic space group Ia{\\overline 3}d and with Si and X cations disordered in the tetrahedral framework sites as typified by dry K 2 MgSi 5 O 12 . Both structure types have tetrahedrally coordinated SiO 4 and XO 4 sharing corners to form a partially substituted silicate framework. Extraframework K + and Rb + cations occupy large channels in the framework. Structural data for the ordered samples show that mean tetrahedral Si-O and X-O bond lengths cover the ranges 1.60 Å (Si-O) to 2.24 Å (Fe 2+ -O) and show an inverse relationship with the intertetrahedral angles (T-O-T) which range from 144.7° (Si-O-Si) to 124.6° (Si-O-Fe 2+ ). For the compositions with both disordered and ordered tetrahedral cation structures (K 2 MgSi 5 O 12 , K 2 CoSi 5 O 12 , K 2 ZnSi 5 O 12 , Rb 2 MnSi 5 O 12 and Cs 2 CuSi 5 O 12 leucites) the disordered polymorphs always have larger unit-cell volumes, larger intertetrahedral T-O-T angles and smaller mean T-O distances than their isochemical ordered polymorphs. The ordered samples clearly have more flexible frameworks than the disordered structures which allow the former to undergo a greater degree of tetrahedral collapse around the interframework cavity cations. Multivariant linear regression has

  14. Electronic and vibrational spectra of matrix isolated anthracene radical cations - Experimental and theoretical aspects

    NASA Technical Reports Server (NTRS)

    Szczepanski, Jan; Vala, Martin; Talbi, Dahbia; Parisel, Olivier; Ellinger, Yves

    1993-01-01

    The IR vibrational and visible/UV electronic absorption spectra of the anthracene cation, An(+), were studied experimentally, in argon matrices at 12 K, as well as theoretically, using ab initio calculations for the vibrational modes and enhanced semiempirical methods with configuration interaction for the electronic spectra. It was found that both approaches predicted well the observed photoelectron spectrum. The theoretical IR intensities showed some remarkable differences between neutral and ionized species (for example, the CH in-plane bending modes and CC in-plane stretching vibrations were predicted to increase by several orders of magnitude upon ionization). Likewise, estimated experimental IR intensities showed a significant increase in the cation band intensities over the neutrals. The implication of these findings for the hypothesis that polycyclic aromatic hydrocarbon cations are responsible for the unidentified IR emission bands from interstellar space is discussed.

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

    NASA Astrophysics Data System (ADS)

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

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

  16. Star-like superalkali cations featuring planar pentacoordinate carbon

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

    Guo, Jin-Chang; Tian, Wen-Juan; Zhao, Xue-Feng

    Superalkali cations, known to possess low vertical electron affinities (VEAs), high vertical detachment energies, and large highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gaps, are intriguing chemical species. Thermodynamically, such species need to be the global minima in order to serve as the promising targets for experimental realization. In this work, we propose the strategies of polyhalogenation and polyalkalination for designing the superalkali cations. By applying these strategies, the local-minimum planar pentacoordinate carbon (ppC) cluster CBe{sub 5} can be modified to form a series of star-like superalkali ppC or quasi-ppC CBe{sub 5}X{sub 5}{sup +} (X = F,more » Cl, Br, Li, Na, K) cations containing a CBe{sub 5} moiety. Polyhalogenation and polyalkalination on the CBe{sub 5} unit may help eliminate the high reactivity of bare CBe{sub 5} molecule by covering the reactive Be atoms with noble halogen anions and alkali cations. Computational exploration of the potential energy surfaces reveals that the star-like ppC or quasi-ppC CBe{sub 5}X{sub 5}{sup +} (X = F, Cl, Br, Li, Na, K) clusters are the true global minima of the systems. The predicted VEAs for CBe{sub 5}X{sub 5}{sup +} range from 3.01 to 3.71 eV for X = F, Cl, Br and 2.12–2.51 eV for X = Li, Na, K, being below the lower bound of the atomic ionization potential of 3.89 eV in the periodic table. Large HOMO-LUMO energy gaps are also revealed for the species: 10.76–11.07 eV for X = F, Cl, Br and 4.99–6.91 eV for X = Li, Na, K. These designer clusters represent the first series of superalkali cations with a ppC center. Bonding analyses show five Be–X–Be three-center two-electron (3c-2e) σ bonds for the peripheral bonding, whereas the central C atom is associated with one 6c-2e π bond and three 6c-2e σ bonds, rendering (π and σ) double aromaticity. Born-Oppenheimer molecular dynamics simulations indicate that the CBe{sub 5} motif is robust in

  17. Oligomeric cationic polymethacrylates: a comparison of methods for determining molecular weight.

    PubMed

    Locock, Katherine E S; Meagher, Laurence; Haeussler, Matthias

    2014-02-18

    This study compares three common laboratory methods, size-exclusion chromatography (SEC), (1)H nuclear magnetic resonance (NMR), and matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF), to determine the molecular weight of oligomeric cationic copolymers. The potential bias for each method was examined across a series of polymers that varied in molecular weight and cationic character (both choice of cation (amine versus guanidine) and relative proportion present). SEC was found to be the least accurate, overestimating Mn by an average of 140%, owing to the lack of appropriate cationic standards available, and the complexity involved in estimating the hydrodynamic volume of copolymers. MALDI-TOF approximated Mn well for the highly monodisperse (Đ < 1.1), low molecular weight (degree of polymerization (DP) <50) species but appeared unsuitable for the largest polymers in the series due to the mass bias associated with the technique. (1)H NMR was found to most accurately estimate Mn in this study, differing to theoretical values by only 5.2%. (1)H NMR end-group analysis is therefore an inexpensive and facile, primary quantitative method to estimate the molecular weight of oliogomeric cationic polymethacrylates if suitably distinct end-groups signals are present in the spectrum.

  18. A conserved π-cation and an electrostatic bridge are essential for 11R-lipoxygenase catalysis and structural stability.

    PubMed

    Eek, Priit; Piht, Mari-Ann; Rätsep, Margus; Freiberg, Arvi; Järving, Ivar; Samel, Nigulas

    2015-10-01

    Lipoxygenases (LOXs) are lipid-peroxidizing enzymes that consist of a regulatory calcium- and membrane-binding PLAT (polycystin-1, lipoxygenase, α-toxin) domain and a catalytic domain. In a previous study, the crystal structure of an 11R-LOX revealed a conserved π-cation bridge connecting these two domains which could mediate the regulatory effect of the PLAT domain to the active site. Here we analyzed the role of residues Trp107 and Lys172 that constitute the π-cation bridge in 11R-LOX along with Arg106 and Asp173-a potential salt bridge, which could also contribute to the inter-domain communication. According to our kinetic assays and protein unfolding experiments conducted using differential scanning fluorimetry and circular dichroism spectroscopy, mutants with a disrupted link display diminished catalytic activity alongside reduced stability of the protein fold. The results demonstrate that both these bridges contribute to the two-domain interface, and are important for proper enzyme activation. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface

    DOE PAGES

    Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin; ...

    2016-06-13

    Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO 3 ) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H 2 O and CO 2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, Sr La ') by the positively charged oxygen vacancies (Vmore » $$••\\atop{o}$$) enriched at the surface. Here we show that reducing the surface V $$••\\atop{o}$$ concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O 2 molecules. We take La 0.8 Sr 0.2 CoO 3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of V $$••\\atop{o}$$ and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a 'volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss.« less

  20. Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface

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

    Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin

    Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO 3 ) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H 2 O and CO 2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, Sr La ') by the positively charged oxygen vacancies (Vmore » $$••\\atop{o}$$) enriched at the surface. Here we show that reducing the surface V $$••\\atop{o}$$ concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O 2 molecules. We take La 0.8 Sr 0.2 CoO 3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of V $$••\\atop{o}$$ and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a 'volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss.« less

  1. Increased Degree of Unsaturation in the Lipid of Antifungal Cationic Amphiphiles Facilitates Selective Fungal Cell Disruption.

    PubMed

    Steinbuch, Kfir B; Benhamou, Raphael I; Levin, Lotan; Stein, Reuven; Fridman, Micha

    2018-05-11

    Antimicrobial cationic amphiphiles derived from aminoglycosides act through cell membrane permeabilization but have limited selectivity for microbial cell membranes. Herein, we report that an increased degree of unsaturation in the fatty acid segment of antifungal cationic amphiphiles derived from the aminoglycoside tobramycin significantly reduced toxicity to mammalian cells. A collection of tobramycin-derived cationic amphiphiles substituted with C 18 lipid chains varying in degree of unsaturation and double bond configuration were synthesized. All had potent activity against a panel of important fungal pathogens including strains with resistance to a variety of antifungal drugs. The tobramycin-derived cationic amphiphile substituted with linolenic acid with three cis double bonds (compound 6) was up to an order of magnitude less toxic to mammalian cells than cationic amphiphiles composed of lipids with a lower degree of unsaturation and than the fungal membrane disrupting drug amphotericin B. Compound 6 was 12-fold more selective (red blood cell hemolysis relative to antifungal activity) than compound 1, the derivative with a fully saturated lipid chain. Notably, compound 6 disrupted the membranes of fungal cells without affecting the viability of cocultured mammalian cells. This study demonstrates that the degree of unsaturation and the configuration of the double bond in lipids of cationic amphiphiles are important parameters that, if optimized, result in compounds with broad spectrum and potent antifungal activity as well as reduced toxicity toward mammalian cells.

  2. Enrofloxacin sorption on smectite clays: effects of pH, cations, and humic acid.

    PubMed

    Yan, Wei; Hu, Shan; Jing, Chuanyong

    2012-04-15

    Enrofloxacin (ENR) occurs widely in natural waters because of its extensive use as a veterinary chemotherapeutic agent. To improve our understanding of the interaction of this emerging contaminant with soils and sediments, sorption of ENR on homoionic smectites and kaolinite was studied as a function of pH, ionic strength, exchangeable cations, and humic acid concentration. Batch experiments and in situ ATR-FTIR analysis suggested multiple sorption mechanisms. Cation exchange was a major contributor to the sorption of cationic ENR species on smectite. The decreased ENR sorption with increasing ionic strength indicated the formation of outer-sphere complexes. Exchangeable cations significantly influenced the sorption capacity, and the observed order was Csa negligible contribution to the interlayer intercalation. The results of this study provide new insight into the molecular mechanisms of ENR sorption on clay minerals. Copyright © 2012 Elsevier Inc. All rights reserved.

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

    PubMed Central

    Lohse, Andrew G.; Hsung, Richard P.

    2011-01-01

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

  4. Cationic antimicrobial peptides inactivate Shiga toxin-encoding bacteriophages

    NASA Astrophysics Data System (ADS)

    Del Cogliano, Manuel E.; Hollmann, Axel; Martinez, Melina; Semorile, Liliana; Ghiringhelli, Pablo D.; Maffía, Paulo C.; Bentancor, Leticia V.

    2017-12-01

    Shiga toxin (Stx) is the principal virulence factor during Shiga toxin-producing Escherichia coli (STEC) infections. We have previously reported the inactivation of bacteriophage encoding Stx after treatment with chitosan, a linear polysaccharide polymer with cationic properties. Cationic antimicrobial peptides (cAMPs) are short linear aminoacidic sequences, with a positive net charge, which display bactericidal or bacteriostatic activity against a wide range of bacterial species. They are promising novel antibiotics since they have shown bactericidal effects against multiresistant bacteria. To evaluate whether cationic properties are responsible for bacteriophage inactivation, we tested seven cationic peptides with proven antimicrobial activity as anti-bacteriophage agents, and one random sequence cationic peptide with no antimicrobial activity as a control. We observed bacteriophage inactivation after incubation with five cAMPs, but no inactivating activity was observed with the random sequence cationic peptide or with the non alpha helical cAMP Omiganan. Finally, to confirm peptide-bacteriophage interaction, zeta potential was analyzed by following changes on bacteriophage surface charges after peptide incubation. According to our results we could propose that: 1) direct interaction of peptides with phage is a necessary step for bacteriophage inactivation, 2) cationic properties are necessary but not sufficient for bacteriophage inactivation, and 3) inactivation by cationic peptides could be sequence (or structure) specific. Overall our data suggest that these peptides could be considered a new family of molecules potentially useful to decrease bacteriophage replication and Stx expression.

  5. Molecular-dynamics simulations of alkaline-earth metal cations in water by atom-bond electronegativity equalization method fused into molecular mechanics.

    PubMed

    Yang, Zhong-Zhi; Li, Xin

    2005-09-01

    Intermolecular potential for alkaline-earth metal (Be(2+), Mg(2+), and Ca(2+)) cations in water has been derived using the atom-bond electronegativity equalization method fused into molecular mechanics (ABEEM/MM), and it is consistent with what was previously applied to the hydration study of the monovalent cations. Parameters for the effective interaction between a cation and a water molecule were determined, reproducing the ab initio results. The static, dynamic, and thermodynamic properties of Be(2+)(aq), Mg(2+)(aq), and Ca(2+)(aq) were studied using these potential parameters. Be(2+) requires a more complicated form of the potential function than Mg(2+) and Ca(2+) in order to obtain better fits. Strong influences of the twofold charged cations on the structures of the hydration shells and some other properties of aqueous ionic solutions are discussed and compared with the results of a previous study of monovalent cations in water. At the same time, comparative study of the hydration properties of each cation is also discussed. This work demonstrates that ABEEM/MM provides a useful tool in the exploration of the hydration of double-charged cations in water.

  6. Calcium Uptake by Excised Maize Roots and Interactions With Alkali Cations 1

    PubMed Central

    Maas, E. V.

    1969-01-01

    Ca2+ uptake was studied in short-term experiments using 5-day-old excised maize roots. This tissue readily absorbs Ca2+, and inhibition by dinitrophenol and low temperature shows that the process is metabolically mediated. The uptake of Ca2+, like that of other cations, is influenced by the counter ion, the pH and concentration of the ambient solution, and the presence of other cations. The rate of uptake from various salts decreases in the following order: NO3− > Cl− = Br− > SO42−. K+ and H+ greatly interfere with Ca2+ absorption, while Li+ and Na+ have only slight effects. PMID:16657169

  7. Permeation of internal and external monovalent cations through the catfish cone photoreceptor cGMP-gated channel

    PubMed Central

    1995-01-01

    The permeation of monovalent cations through the cGMP-gated channel of catfish cone outer segments was examined by measuring permeability and conductance ratios under biionic conditions. For monovalent cations presented on the cytoplasmic side of the channel, the permeability ratios with respect to extracellular Na followed the sequence NH4 > K > Li > Rb = Na > Cs while the conductance ratios at +50 mV followed the sequence Na approximately NH4 > K > Rb > Li = Cs. These patterns are broadly similar to the amphibian rod channel. The symmetry of the channel was tested by presenting the test ion on the extracellular side and using Na as the common reference ion on the cytoplasmic side. Under these biionic conditions, the permeability ratios with respect to Na at the intracellular side followed the sequence NH4 > Li > K > Na > Rb > Cs while the conductance ratios at +50 mV followed the sequence NH4 > K approximately Na > Rb > Li > Cs. Thus, the channel is asymmetric with respect to external and internal cations. Under symmetrical 120 mM ionic conditions, the single-channel conductance at +50 mV ranged from 58 pS in NH4 to 15 pS for Cs and was in the order NH4 > Na > K > Rb > Cs. Unexpectedly, the single-channel current-voltage relation showed sufficient outward rectification to account for the rectification observed in multichannel patches without invoking voltage dependence in gating. The concentration dependence of the reversal potential for K showed that chloride was impermeant. Anomalous mole fraction behavior was not observed, nor, over a limited concentration range, were multiple dissociation constants. An Eyring rate theory model with a single binding site was sufficient to explain these observations. PMID:8786344

  8. Operational Site Selection for Unmanned Aircraft

    DTIC Science & Technology

    2011-06-01

    eliminate unsuitable areas, the Op Site Selection process must first consider landcover , terrain, and specifications for one or more UAS platforms...areas, the OSS process must first consider landcover , terrain, and specifi- cations for one or more UAS platforms. To select the most optimal sites, the...by landcover , ERDC/CERL TR-11-16 2 soil type, slope, and aspect. The individual terrain units are pre- determined and delineated by a separate

  9. A weak cation-exchange monolith as stationary phase for the separation of peptide diastereomers by CEC.

    PubMed

    Ludewig, Ronny; Nietzsche, Sandor; Scriba, Gerhard K E

    2011-01-01

    A CEC weak cation-exchange monolith has been prepared by in situ polymerization of acrylamide, methylenebisacrylamide and 4-acrylamidobutyric acid in a decanol-dimethylsulfoxide mixture as porogen. The columns were evaluated by SEM and characterized with regard to the separation of diastereomers and α/β-isomers of aspartyl peptides. Column preparation was reproducible as evidenced by comparison of the analyte retention times of several columns prepared simultaneously. Analyte separation was achieved using mobile phases consisting of acidic phosphate buffer and ACN. Under these conditions the peptides migrated due to their electrophoretic mobility but the EOF also contributed as driving force as a function of the pH of the mobile phase due to increasing dissociation of the carboxyl groups of the polymer. Raising the pH of the mobile phase also resulted in deprotonation of the peptides reducing analyte mobility. Due to these mechanisms each pair of diastereomeric peptides displayed the highest resolution at a different pH of the buffer component of the mobile phase. Comparing the weak-cation exchange monolith to an RP monolith and a strong cation-exchange monolith different elution order of some peptide diastereomers was observed, clearly illustrating that interactions with the stationary phase contribute to the CEC separations. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Binding symmetry of extracellular divalent cations to conduction pore studied using tandem dimers of a CNG channel.

    PubMed

    Kwon, Ryuk-Jun; Ha, Tal Soo; Kim, Wonjae; Park, Chul-Seung

    2002-11-08

    Cyclic nucleotide-gated (CNG) channels are composed of the tetramer of alpha-subunit alone or alpha- and beta-subunits. The alpha-subunits of these channels have a conserved glutamate (Glu) residue within the pore-forming region and the residue determines the selectivity as well as the affinity for the extracellular divalent cations. Using the high-affinity mutant (E363D) of bovine retinal CNG channel in which the Glu at position 363 was replaced to Asp, we constructed tandem dimers and investigated the binding characteristics of divalent cations to the site. The gating and permeation characteristics of individual homomeric tandem dimers are indistinguishable to those of homo-tetramers formed by parental monomers. The heteromeric tandem dimers showed the binding affinity for Sr(2+) identical to the geometric mean of the affinities for two parent channels, indicating the energy additive and thus the simultaneous interaction. On the other hand, the binding affinity for Mg(2+) followed the harmonic mean of those parent channels indicating that Mg(2+) interacts more strongly with the subunit bearing Asp residue at the position. Thus the results strongly suggest that the Glu363 residues in the CNG channel pore be flexible enough to adapt different binding symmetries for different divalent cations. Moreover, the simultaneous interaction between the four Glu residues and Sr(2+) provides an important structural constraint to the CNG channel outer vestibule of unknown structure.

  11. 75 FR 41237 - Public Land Order No. 7745; Partial Revocation of Power Site Reserve Nos. 510 and No. 515; Montana

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-07-15

    ... MTM 41534] Public Land Order No. 7745; Partial Revocation of Power Site Reserve Nos. 510 and No. 515... of public lands withdrawn for Power Site Reserve Nos. 510 and 515. This order also opens the lands to... INFORMATION: The Bureau of Land Management has determined that portions of Power Site Reserve Nos. 510 and 515...

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

    PubMed

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

    2015-03-07

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

  13. 21 CFR 872.3480 - Polyacrylamide polymer (modified cationic) denture adhesive.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Polyacrylamide polymer (modified cationic) denture... polymer (modified cationic) denture adhesive. (a) Identification. A polyacrylamide polymer (modified cationic) denture adhesive is a device composed of polyacrylamide polymer (modified cationic) intended to...

  14. 21 CFR 872.3480 - Polyacrylamide polymer (modified cationic) denture adhesive.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Polyacrylamide polymer (modified cationic) denture... polymer (modified cationic) denture adhesive. (a) Identification. A polyacrylamide polymer (modified cationic) denture adhesive is a device composed of polyacrylamide polymer (modified cationic) intended to...

  15. 21 CFR 872.3480 - Polyacrylamide polymer (modified cationic) denture adhesive.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Polyacrylamide polymer (modified cationic) denture... polymer (modified cationic) denture adhesive. (a) Identification. A polyacrylamide polymer (modified cationic) denture adhesive is a device composed of polyacrylamide polymer (modified cationic) intended to...

  16. 21 CFR 872.3480 - Polyacrylamide polymer (modified cationic) denture adhesive.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Polyacrylamide polymer (modified cationic) denture... polymer (modified cationic) denture adhesive. (a) Identification. A polyacrylamide polymer (modified cationic) denture adhesive is a device composed of polyacrylamide polymer (modified cationic) intended to...

  17. 21 CFR 872.3480 - Polyacrylamide polymer (modified cationic) denture adhesive.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Polyacrylamide polymer (modified cationic) denture... polymer (modified cationic) denture adhesive. (a) Identification. A polyacrylamide polymer (modified cationic) denture adhesive is a device composed of polyacrylamide polymer (modified cationic) intended to...

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

    PubMed

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

    2015-01-01

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

  19. Ionophores and receptors using cation-pi interactions: collarenes.

    PubMed

    Choi, H S; Suh, S B; Cho, S J; Kim, K S

    1998-10-13

    Cation-pi interactions are important forces in molecular recognition by biological receptors, enzyme catalysis, and crystal engineering. We have harnessed these interactions in designing molecular systems with circular arrangement of benzene units that are capable of acting as ionophores and models for biological receptors. [n]Collarenes are promising candidates with high selectivity for a specific cation, depending on n, because of their structural rigidity and well-defined cavity size. The interaction energies of [n]collarenes with cations have been evaluated by using ab initio calculations. The selectivity of these [n]collarenes in aqueous solution was revealed by using statistical perturbation theory in conjunction with Monte Carlo and molecular dynamics simulations. It has been observed that in [n]collarenes the ratio of the interaction energies of a cation with it and the cation with the basic building unit (benzene) can be correlated to its ion selectivity. We find that collarenes are excellent and efficient ionophores that bind cations through cation-pi interactions. [6]Collarene is found to be a selective host for Li+ and Mg2+, [8]collarene for K+ and Sr2+, and [10]collarene for Cs+ and Ba2+. This finding indicates that [10]collarene and [8]collarene could be used for effective separation of highly radioactive isotopes, 137Cs and 90Sr, which are major constituents of nuclear wastes. More interestingly, collarenes of larger cavity size can be useful in capturing organic cations. [12]Collarene exhibits a pronounced affinity for tetramethylammonium cation and acetylcholine, which implies that it could serve as a model for acetylcholinestrase. Thus, collarenes can prove to be novel and effective ionophores/model-receptors capable of heralding a new direction in molecular recognition and host-guest chemistry.

  20. On two alternative mechanisms of ethane activation over ZSM-5 zeolite modified by Zn2+ and Ga1+ cations.

    PubMed

    Kazansky, V B; Subbotina, I R; Rane, N; van Santen, R A; Hensen, E J M

    2005-08-21

    The activation of ethane over zinc- and gallium-modified HZSM-5 dehydrogenation catalysts was studied by diffuse reflectance infrared spectroscopy. Hydrocarbon activation on HZSM-5 modified by bivalent Zn and univalent Ga cations proceeds via two distinctly different mechanisms. The stronger molecular adsorption of ethane by the acid-base pairs formed by distantly separated cationic Zn2+ and basic oxygen sites results already at room temperature in strong polarizability of adsorbed ethane and subsequent heterolytic dissociative adsorption at moderate temperatures. In contrast, molecular adsorption of ethane on Ga+ cations is weak. At high temperatures dissociative hydrocarbon adsorption takes place, resulting in the formation of ethyl and hydride fragments coordinating to the cationic gallium species. Whereas in the zinc case a Brønsted acid proton is formed upon ethane dissociation, decomposition of the ethyl fragment on gallium results in gallium dihydride species and does not lead to Brønsted acid protons. This difference in alkane activation has direct consequences for hydrocarbon conversions involving dehydrogenation.

  1. Isomerization and fragmentation reactions of gaseous phenylarsane radical cations and phenylarsanyl cations. A study by tandem mass spectrometry and theoretical calculations.

    PubMed

    Letzel, Matthias; Kirchhoff, Dirk; Grützmacher, Hans-Friedrich; Stein, Daniel; Grützmacher, Hansjörg

    2006-04-28

    The unimolecular reactions of radical cations and cations derived from phenylarsane, C6H5AsH2 (1) and dideutero phenylarsane, C6H5AsD2 (1-d2), were investigated by methods of tandem mass spectrometry and theoretical calculations. The mass spectrometric experiments reveal that the molecular ion of phenylarsane, 1*+, exhibits different reactivity at low and high internal excess energy. Only at low internal energy the observed fragmentations are as expected, that is the molecular ion 1*+ decomposes almost exclusively by loss of an H atom. The deuterated derivative 1-d2 with an AsD2 group eliminates selectively a D atom under these conditions. The resulting phenylarsenium ion [C6H5AsH]+, 2+, decomposes rather easily by loss of the As atom to give the benzene radical cation [C6H6]*+ and is therefore of low abundance in the 70 eV EI mass spectrum. At high internal excess energy, the ion 1*+ decomposes very differently either by elimination of an H2 molecule, or by release of the As atom, or by loss of an AsH fragment. Final products of these reactions are either the benzoarsenium ion 4*+, or the benzonium ion [C6H7]+, or the benzene radical cation, [C6H6]*+. As key-steps, these fragmentations contain reductive eliminations from the central As atom under H-H or C-H bond formation. Labeling experiments show that H/D exchange reactions precede these fragmentations and, specifically, that complete positional exchange of the H atoms in 1*+ occurs. Computations at the UMP2/6-311+G(d)//UHF/6-311+G(d) level agree best with the experimental results and suggest: (i) 1*+ rearranges (activation enthalpy of 93 kJ mol(-1)) to a distinctly more stable (DeltaH(r)(298) = -64 kJ mol(-1)) isomer 1 sigma*+ with a structure best represented as a distonic radical cation sigma complex between AsH and benzene. (ii) The six H atoms of the benzene moiety of 1 sigma*+ become equivalent by a fast ring walk of the AsH group. (iii) A reversible isomerization 1+<==>1 sigma*+ scrambles eventually all H

  2. Identification and characterization of the sodium-binding site of activated protein C.

    PubMed

    He, X; Rezaie, A R

    1999-02-19

    Activated protein C (APC) requires both Ca2+ and Na+ for its optimal catalytic function. In contrast to the Ca2+-binding sites, the Na+-binding site(s) of APC has not been identified. Based on a recent study with thrombin, the 221-225 loop is predicted to be a potential Na+-binding site in APC. The sequence of this loop is not conserved in trypsin. We engineered a Gla domainless form of protein C (GDPC) in which the 221-225 loop was replaced with the corresponding loop of trypsin. We found that activated GDPC (aGDPC) required Na+ (or other alkali cations) for its amidolytic activity with dissociation constant (Kd(app)) = 44.1 +/- 8.6 mM. In the presence of Ca2+, however, the requirement for Na+ by aGDPC was eliminated, and Na+ stimulated the cleavage rate 5-6-fold with Kd(app) = 2.3 +/- 0.3 mM. Both cations were required for efficient factor Va inactivation by aGDPC. In the presence of Ca2+, the catalytic function of the mutant was independent of Na+. Unlike aGDPC, the mutant did not discriminate among monovalent cations. We conclude that the 221-225 loop is a Na+-binding site in APC and that an allosteric link between the Na+ and Ca2+ binding loops modulates the structure and function of this anticoagulant enzyme.

  3. Effect of cations in the background electrolyte on the adsorption kinetics of copper and cadmium and the isoelectric point of imogolite.

    PubMed

    Arancibia-Miranda, Nicolás; Silva-Yumi, Jorge; Escudey, Mauricio

    2015-12-15

    Modification of surface charge and changes in the isoelectric point (IEP) of synthetic imogolite were studied for various cations in the background electrolyte (K(+), NH4(+), Mg(2+), and Ca(2+)). From the electrophoretic mobility data, it was established that the K(+) (KCl) concentration does not affect the IEP of imogolite; therefore, KCl is a suitable background electrolyte. In terms of the magnitude of changes in the IEP and surface charge, the cations may be ranked in the following order: Mg(2+)≈Ca(2+)>NH4(+)>K(+). Four different kinetic models were used to evaluate the influence of Mg(2+), Ca(2+), NH4(+), and K(+) on the adsorption of Cd and Cu on synthetic imogolite. When adsorption occurs in the presence of cations with the exception of K(+), the kinetics of the process is well described by the pseudo-first order model. On the other hand, when adsorption is conducted in the presence of K(+), the adsorption kinetics is well described by the pseudo-second order, Elovich, and Weber-Morris models. From the surface charge measurements, the affinity between imogolite and the cations and their effect on the adsorption of trace elements, namely Cu and Cd, were established. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Silver Niobate Lead-Free Antiferroelectric Ceramics: Enhancing Energy Storage Density by B-Site Doping.

    PubMed

    Zhao, Lei; Gao, Jing; Liu, Qing; Zhang, Shujun; Li, Jing-Feng

    2018-01-10

    Lead-free dielectric ceramics with high recoverable energy density are highly desired to sustainably meet the future energy demand. AgNbO 3 -based lead-free antiferroelectric ceramics with double ferroelectric hysteresis loops have been proved to be potential candidates for energy storage applications. Enhanced energy storage performance with recoverable energy density of 3.3 J/cm 3 and high thermal stability with minimal energy density variation (<10%) over a temperature range of 20-120 °C have been achieved in W-modified AgNbO 3 ceramics. It is revealed that the W 6+ cations substitute the B-site Nb 5+ and reduce the polarizability of B-site cations, leading to the enhanced antiferroelectricity, which is confirmed by the polarization hysteresis and dielectric tunability. It is believed that the polarizability of B-site cations plays a dominant role in stabilizing the antiferroelectricity in AgNbO 3 system, in addition to the tolerance factor, which opens up a new design approach to achieve stable antiferroelectric materials.

  5. Effect of Dialkyl Ammonium Cationic Surfactants on the Microfluidity of Membranes Containing Raft Domains.

    PubMed

    Uyama, Makoto; Inoue, Kaori; Kinoshita, Koichi; Miyahara, Reiji; Yokoyama, Hirokazu; Nakano, Minoru

    2018-01-01

    It has been reported that a lot of receptors localize in lipid raft domains and that the microfluidity of these domains regulates the activation of these receptors. In this study, we focused on the lipid raft and in order to evaluate the physicochemical effects of surfactants on microfluidity of lipid membranes, we used liposomes comprising of egg-yolk L-α-phosphatidylcholine, egg-yolk sphingomyelin, and cholesterol as a model of cell membranes containing raft domains. The microfluidity of the domains was characterized by fluorescence spectrometry using 1,6-diphenyl-1,3,5-hexatriene and 2-dimethylamino-6-lauroylnaphthalene. Among several surfactants, dialkylammonium-type cationic surfactants most efficiently increased the microfluidity. It is therefore concluded that (1) the electrostatic interaction between the cationic surfactant and eggPC/eggSM/cholesterol liposome could be important, (2) surfactants with alkyl chains more effectively inserted into membranes than those with acyl chains, and (3) cationic surfactants with lower T m values have a greater ability to increase the fluidity.

  6. Flocculation and antimicrobial properties of a cationized starch.

    PubMed

    Liu, Zhouzhou; Huang, Mu; Li, Aimin; Yang, Hu

    2017-08-01

    In this study, a series of cationized starch-based flocculants (starch-3-chloro-2-hydroxypropyl triethyl ammonium chloride, St-CTA) containing various quaternary ammonium salt groups on the starch backbone were prepared using a simple etherification reaction. All of the prepared starch-based flocculants show effective performance for the flocculation of kaolin suspension, two bacterial (Escherichia coli and Staphylococcus aureus) suspensions, and two contaminant mixtures (kaolin and each bacterium) under most pH conditions. St-CTA with a high substitution degree of CTA demonstrates improved contaminant removal efficiency because of the strong cationic nature of the grafted quaternary ammonium salt groups and the charge naturalization flocculation effect. The antibacterial effects of St-CTA were also evaluated, considering that many quaternary ammonium salt compounds elicit bactericidal effects. Three-dimensional excitation-emission matrix spectra and direct cell morphological observation under scanning electron microscopy reveal that the starch-based flocculants exhibit better antibacterial effects on the Gram-negative bacterium E. coli than on the Gram-positive bacterium S. aureus. The thicker cell wall due to the presence of abundant peptidoglycan and teichoic acids of S. aureus than E. coli explains the uneasy breakage of S. aureus cell wall after being attacked by the cationized starch-based flocculants. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. A Visible Light Initiating System for Free Radical Promoted Cationic Polymerization

    DTIC Science & Technology

    1994-02-02

    identify the end groups in the polymer of cyclohexene oxide. N,N-Dimethylnaphthyl amine (DNA), a compound with high fluorescence quantum yield, was used...candidates to be polymerized via a cationic mechanism include cyclic ethers, cyclic formals and acetals, vinyl ethers, and epoxy compounds . Of these...reported sensitizer, bears two dimethylamino groups, is direct evidence that an aromatic amine can be present in a cationically photopolymerizable system

  8. Site Dependency of the High Conductivity of Ga 2 In 6 Sn 2 O 16 : The Role of the 7-Coordinate Site

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

    Rickert, Karl; Huq, Ashfia; Lapidus, Saul H.

    The 6-coordinated cation site is the fundamental building block of the most effective transparent conducting oxides. Ga2In6Sn2O16, however, maintains 4-, 6-, 7-, and 8-coordinated cation sites and still exhibits desirable transparency and high conductivity. To investigate the potential impact of these alternative sites, we partially replace the Sn in Ga2In6Sn2O16 with Ti, Zr, or Hf and use a combined approach of DFT-based calculations, X-ray diffraction, and neutron diffraction to establish that the substitution occurs preferentially on the 7-coordinate site. In contrast to Sn, the empty d orbitals of Ti, Zr, and Hf promote spd covalency with the surrounding oxygen whichmore » decreases the conductivity. Pairing the substitutional site preference with the magnitude of this decrease demonstrates that the 7-coordinate site is the major contributor to the conductivity. The optical band gaps, in contrast, are shown to be site independent and composition dependent. Continued replacement of Sn after all 7-coordinate Sn has been substituted results in the formation of a 7-coordinate In antisite or replacement of 6-coordinate Sn, depending on the identity of the d0 substitute.« less

  9. Site Dependency of the High Conductivity of Ga 2 In 6 Sn 2 O 16 : The Role of the 7-Coordinate Site

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

    Rickert, Karl; Huq, Ashfia; Lapidus, Saul H.

    In 6-coordinated cation sites, we find that it is the fundamental building block of the most effective transparent conducting oxides. Ga 2In 6SnO 16, however, maintains 4-, 6-, 7-, and 8-coordinated cation sites and still exhibits desirable transparency and high conductivity. To investigate the potential impact of these alternative sites, we partially replace the Sn in Ga 2In 6Sn 2O 16 with Ti, Zr, or Hf and use a combined approach of density functional theory-based calculations, X-ray diffraction, and neutron diffraction to establish that the substitution occurs preferentially on the 7-coordinate site. Conversely to Sn, the empty d orbitals ofmore » Ti, Zr, and Hf promote spd covalency with the surrounding oxygen, which decreases the conductivity. Pairing the substitutional site preference with the magnitude of this decrease demonstrates that the 7-coordinate site is the V major contributor to conductivity. The optical band gaps, in contrast, are shown to be site-independent and composition-dependent. After all 7-coordinate Sn has been replaced, the continued substitution of Sn results in the formation of a 7-coordinate In antisite or replacement of 6-coordinate Sn, depending on the identity of the d(0) substitute.« less

  10. Site Dependency of the High Conductivity of Ga 2 In 6 Sn 2 O 16 : The Role of the 7-Coordinate Site

    DOE PAGES

    Rickert, Karl; Huq, Ashfia; Lapidus, Saul H.; ...

    2015-11-11

    In 6-coordinated cation sites, we find that it is the fundamental building block of the most effective transparent conducting oxides. Ga 2In 6SnO 16, however, maintains 4-, 6-, 7-, and 8-coordinated cation sites and still exhibits desirable transparency and high conductivity. To investigate the potential impact of these alternative sites, we partially replace the Sn in Ga 2In 6Sn 2O 16 with Ti, Zr, or Hf and use a combined approach of density functional theory-based calculations, X-ray diffraction, and neutron diffraction to establish that the substitution occurs preferentially on the 7-coordinate site. Conversely to Sn, the empty d orbitals ofmore » Ti, Zr, and Hf promote spd covalency with the surrounding oxygen, which decreases the conductivity. Pairing the substitutional site preference with the magnitude of this decrease demonstrates that the 7-coordinate site is the V major contributor to conductivity. The optical band gaps, in contrast, are shown to be site-independent and composition-dependent. After all 7-coordinate Sn has been replaced, the continued substitution of Sn results in the formation of a 7-coordinate In antisite or replacement of 6-coordinate Sn, depending on the identity of the d(0) substitute.« less

  11. Prediction of Ordered Water Molecules in Protein Binding Sites from Molecular Dynamics Simulations: The Impact of Ligand Binding on Hydration Networks.

    PubMed

    Rudling, Axel; Orro, Adolfo; Carlsson, Jens

    2018-02-26

    Water plays a major role in ligand binding and is attracting increasing attention in structure-based drug design. Water molecules can make large contributions to binding affinity by bridging protein-ligand interactions or by being displaced upon complex formation, but these phenomena are challenging to model at the molecular level. Herein, networks of ordered water molecules in protein binding sites were analyzed by clustering of molecular dynamics (MD) simulation trajectories. Locations of ordered waters (hydration sites) were first identified from simulations of high resolution crystal structures of 13 protein-ligand complexes. The MD-derived hydration sites reproduced 73% of the binding site water molecules observed in the crystal structures. If the simulations were repeated without the cocrystallized ligands, a majority (58%) of the crystal waters in the binding sites were still predicted. In addition, comparison of the hydration sites obtained from simulations carried out in the absence of ligands to those identified for the complexes revealed that the networks of ordered water molecules were preserved to a large extent, suggesting that the locations of waters in a protein-ligand interface are mainly dictated by the protein. Analysis of >1000 crystal structures showed that hydration sites bridged protein-ligand interactions in complexes with different ligands, and those with high MD-derived occupancies were more likely to correspond to experimentally observed ordered water molecules. The results demonstrate that ordered water molecules relevant for modeling of protein-ligand complexes can be identified from MD simulations. Our findings could contribute to development of improved methods for structure-based virtual screening and lead optimization.

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

    PubMed Central

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

    2011-01-01

    A combination of explicit solvent molecular dynamics simulation (30 simulations reaching 4 µs in total), hybrid quantum mechanics/molecular mechanics approach and isothermal titration calorimetry was used to investigate the atomistic picture of ion binding to 15-mer thrombin-binding quadruplex DNA (G-DNA) aptamer. Binding of ions to G-DNA is complex multiple pathway process, which is strongly affected by the type of the cation. The individual ion-binding events are substantially modulated by the connecting loops of the aptamer, which play several roles. They stabilize the molecule during time periods when the bound ions are not present, they modulate the route of the ion into the stem and they also stabilize the internal ions by closing the gates through which the ions enter the quadruplex. Using our extensive simulations, we for the first time observed full spontaneous exchange of internal cation between quadruplex molecule and bulk solvent at atomistic resolution. The simulation suggests that expulsion of the internally bound ion is correlated with initial binding of the incoming ion. The incoming ion then readily replaces the bound ion while minimizing any destabilization of the solute molecule during the exchange. PMID:21893589

  13. Cellular cation transport studied by 6/7Li and 23Na NMR in a porous Mo132 Keplerate type nano-capsule as model system.

    PubMed

    Rehder, Dieter; Haupt, Erhard T K; Müller, Achim

    2008-01-01

    Li+ ions can interplay with other cations intrinsically present in the intra- and extra-cellular space (i.e. Na+, K+, Mg2+ and Ca2+) have therapeutic effects (e.g. in the treatment of bipolar disorder) or toxic effects (at higher doses), likely because Li+ interferes with the intra-/extra-cellular concentration gradients of the mentioned physiologically relevant cations. The cellular transmembrane transport can be modelled by molybdenum-oxide-based Keplerates, i.e. nano-sized porous capsules containing 132 Mo centres, monitored through 6/7Li as well as 23Na NMR spectroscopy. The effects on the transport of Li+ cations through the 'ion channels' of these model cells, caused by variations in water amount, temperature, and by the addition of organic cationic 'plugs' and the shift reagent [Dy(PPP)2](7-) are reported. In the investigated solvent systems, water acts as a transport mediator for Li+. Likewise, the counter-transport (Li+/Na+, Li+/K+, Li+/Cs+ and Li+/Ca2+) has been investigated by 7Li NMR and, in the case of Li+/Na+ exchange, by 23Na NMR, and it has been shown that most (in the case of Na+ and K+, all (Ca2+) or almost none (Cs+) of the Li cations is extruded from the internal sites of the artificial cell to the extra-cellular medium, while Na+, K+ and Ca2+ are partially incorporated.

  14. Immune complexes with cationic antibodies deposit in glomeruli more effectively than cationic antibodies alone.

    PubMed

    Mannik, M; Gauthier, V J; Stapleton, S A; Agodoa, L Y

    1987-06-15

    In previously published studies, highly cationized antibodies alone and in immune complexes bound to glomeruli by charge-charge interaction, but only immune complexes persisted in glomeruli. Because normal IgG does not deposit in glomeruli, studies were conducted to determine whether cationized antibodies can be prepared which deposit in glomeruli when bound to antigen but not when free in circulation. A series of cationized rabbit antiHSA was prepared with the number of added amino groups ranging from 13.3 to 60.2 per antibody molecule. Antibodies alone or in preformed soluble immune complexes, prepared at fivefold or 50-fold antigen excess, were administered to mice. With the injection of a fixed dose of 100 micrograms per mouse, antibodies alone did not deposit in glomeruli with less than 29.6 added amino groups by immunofluorescence microscopy. In contrast, 100 micrograms of antibodies with 23.5 added amino groups in immune complexes, made at fivefold antigen excess, formed immune deposits in glomeruli. With selected preparations of cationized, radiolabeled antibodies, deposition in glomeruli was quantified by isolation of mouse glomeruli. These quantitative data were in good agreement with the results of immunofluorescence microscopy. Immune complexes made at 50-fold antigen excess, containing only small-latticed immune complexes with no more than two antibody molecules per complex, deposited in glomeruli similar to antibodies alone. Selected cationized antibodies alone or in immune complexes were administered to mice in varying doses. In these experiments, glomerular deposition of immune complexes, made at fivefold antigen excess, was detected with five- to 10-fold smaller doses than the deposition of the same antibodies alone. These studies demonstrate that antibody molecules in immune complexes are more likely to deposit in glomeruli by charge-charge interactions than antibodies alone.

  15. High-performance cation-exchange chromatofocusing of proteins.

    PubMed

    Kang, Xuezhen; Frey, Douglas D

    2003-03-28

    Chromatofocusing using high-performance cation-exchange column packings, as opposed to the more commonly used anion-exchange column packings, is investigated with regard to the performance achieved and the range of applications possible. Linear or convex gradients in the range from pH 2.6 to 9 were formed using a variety of commercially available column packings that provide a buffering capacity in different pH ranges, and either polyampholytes or simple mixtures having a small number (three or fewer) of buffering species as the elution buffer. The resolutions achieved using cation-exchange or anion-exchange chromatofocusing were in general comparable, although for certain pairs of proteins better resolution could be achieved using one type of packing as compared to the other, evidently due to the way electrostatic charges are distributed on the protein surface. Several chromatofocusing methods were investigated that take advantage of the acid-base properties of commercially available cation-exchange column packings. These include the use of gradients with a composite shape, the use of very low pH ranges, and the use of elution buffers containing a single buffering species. The advantages of chromatofocusing over ion-exchange chromatography using a salt gradient at constant pH were illustrated by employing the former method and a cation-exchange column packing to separate beta-lactoglobulins A and B, which is a separation reported to be impossible using the latter method and a cation-exchange column packing. Trends in the apparent isoelectric points determined using cation- and anion-exchange chromatofocusing were interpreted using applicable theories. Results of this study indicate that cation-exchange chromatofocusing is a useful technique which is complementary to anion-exchange chromatofocusing and isoelectric focusing for separating proteins at both the analytical and preparative scales.

  16. Reaction enthalpy from the binding of multivalent cations to anionic polyelectrolytes in dilute solutions

    NASA Astrophysics Data System (ADS)

    Hansch, Markus; Kaub, Hans Peter; Deck, Sascha; Carl, Nico; Huber, Klaus

    2018-03-01

    Dilute solutions of sodium poly(styrene sulfonate) (NaPSS) in the presence of Al3+, Ca2+, and Ba2+ were analysed by means of isothermal titration calorimetry (ITC) in order to investigate the heat effect of bond formation between those cations and the anionic SO3- residues of NaPSS. The selection of the cations was guided by the solution behavior of the corresponding PSS salts from a preceding study [M. Hansch et al., J. Chem. Phys. 148(1), 014901 (2018)], where bonds between Ba2+ and anionic PSS showed an increasing solubility with decreasing temperature and Al3+ exhibited the inverse trend. Unlike to Al3+ and Ba2+, Ca2+ is expected to behave as a purely electrostatically interacting bivalent cation and was thus included in the present study. Results from ITC satisfactorily succeeded to explain the temperature-dependent solution behavior of the salts with Al3+ and Ba2+ and confirmed the non-specific behavior of Ca2+. Additional ITC experiments with salts of Ca2+ and Ba2+ and sodium poly(acrylate) complemented the results on PSS by data from a chemically different polyanion. Availability of these joint sets of polyanion-cation combinations not only offers the chance to identify common features and subtle differences in the solution behavior of polyelectrolytes in the presence of multi-valent cations but also points to a new class of responsive materials.

  17. Process and apparatus for the production of BI-213 cations

    DOEpatents

    Horwitz, E. Philip; Hines, John J.; Chiarizia, Renato; Dietz, Mark

    1998-01-01

    A process for producing substantially impurity-free Bi-213 cations is disclosed. An aqueous acid feed solution containing Ac-225 cations is contacted with an ion exchange medium to bind the Ac-225 cations and form an Ac-225-laden ion exchange medium. The bound Ac-225 incubates on the ion exchange medium to form Bi-213 cations by radioactive decay. The Bi-213 cations are then recovered from the Ac-225-laden ion exchange medium to form a substantially impurity-free aqueous Bi-213 cation acid solution. An apparatus for carrying out this process is also disclosed.

  18. Process and apparatus for the production of Bi-213 cations

    DOEpatents

    Horwitz, E.P.; Hines, J.J.; Chiarizia, R.; Dietz, M.

    1998-12-29

    A process for producing substantially impurity-free Bi-213 cations is disclosed. An aqueous acid feed solution containing Ac-225 cations is contacted with an ion exchange medium to bind the Ac-225 cations and form an Ac-225-laden ion exchange medium. The bound Ac-225 incubates on the ion exchange medium to form Bi-213 cations by radioactive decay. The Bi-213 cations are then recovered from the Ac-225-laden ion exchange medium to form a substantially impurity-free aqueous Bi-213 cation acid solution. An apparatus for carrying out this process is also disclosed. 7 figs.

  19. Electronic structure of the benzene dimer cation

    NASA Astrophysics Data System (ADS)

    Pieniazek, Piotr A.; Krylov, Anna I.; Bradforth, Stephen E.

    2007-07-01

    The benzene and benzene dimer cations are studied using the equation-of-motion coupled-cluster model with single and double substitutions for ionized systems. The ten lowest electronic states of the dimer at t-shaped, sandwich, and displaced sandwich configurations are described and cataloged based on the character of the constituent fragment molecular orbitals. The character of the states, bonding patterns, and important features of the electronic spectrum are explained using qualitative dimer molecular orbital linear combination of fragment molecular orbital framework. Relaxed ground state geometries are obtained for all isomers. Calculations reveal that the lowest energy structure of the cation has a displaced sandwich structure and a binding energy of 20kcal/mol, while the t-shaped isomer is 6kcal/mol higher. The calculated electronic spectra agree well with experimental gas phase action spectra and femtosecond transient absorption in liquid benzene. Both sandwich and t-shaped structures feature intense charge resonance bands, whose location is very sensitive to the interfragment distance. Change in the electronic state ordering was observed between σ and πu states, which correlate to the B˜ and C˜ bands of the monomer, suggesting a reassignment of the local excitation peaks in the gas phase experimental spectrum.

  20. Study of lithium cation in water clusters: based on atom-bond electronegativity equalization method fused into molecular mechanics.

    PubMed

    Li, Xin; Yang, Zhong-Zhi

    2005-05-12

    We present a potential model for Li(+)-water clusters based on a combination of the atom-bond electronegativity equalization and molecular mechanics (ABEEM/MM) that is to take ABEEM charges of the cation and all atoms, bonds, and lone pairs of water molecules into the intermolecular electrostatic interaction term in molecular mechanics. The model allows point charges on cationic site and seven sites of an ABEEM-7P water molecule to fluctuate responding to the cluster geometry. The water molecules in the first sphere of Li(+) are strongly structured and there is obvious charge transfer between the cation and the water molecules; therefore, the charge constraint on the ionic cluster includes the charged constraint on the Li(+) and the first-shell water molecules and the charge neutrality constraint on each water molecule in the external hydration shells. The newly constructed potential model based on ABEEM/MM is first applied to ionic clusters and reproduces gas-phase state properties of Li(+)(H(2)O)(n) (n = 1-6 and 8) including optimized geometries, ABEEM charges, binding energies, frequencies, and so on, which are in fair agreement with those measured by available experiments and calculated by ab initio methods. Prospects and benefits introduced by this potential model are pointed out.

  1. Production of iota toxin by Clostridium spiroforme: a requirement for divalent cations.

    PubMed

    Carman, R J; van Tassell, R L; Wilkins, T D

    1987-10-01

    The effects of divalent cations (Ca2+, Co2+ and Zn2+) on the production of iota toxin by Clostridium spiroforme were studied. Toxin production had an absolute requirement for one or more cations in the range 1-5 mM. Using bispecific antisera, we showed that production of both the components of the toxin (ia and ib) were enhanced by divalent cations added to brain-heart infusion supplemented with peptone and glucose.

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

    PubMed

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

    2015-04-28

    Clay minerals saturated with different exchangeable cations are expected to play various roles in photodegradation of polycyclic aromatic hydrocarbons (PAHs) via direct and/or indirect pathways on clay surfaces. In the present study, anthracene and phenanthrene were selected as molecule probes to investigate the roles of exchangeable cations on their photodegradation under visible light irradiation. For five types of cation-modified smectite clays, the photodegradation rate of anthracene and phenanthrene follows the order: Fe(3+)>Al(3+)>Cu(2+)>Ca(2+)>K(+)>Na(+), which is consistent with the binding energy of cation-π interactions between PAHs and exchangeable cations. The result suggests that PAHs photolysis rate depends on cation-π interactions on clay surfaces. Meanwhile, the deposition of anthracene at the Na(+)-smectite and K(+)-smectite surface favors solar light absorption, resulting in enhanced direct photodecomposition of PAHs. On the other hand, smectite clays saturated with Fe(3+), Al(3+), and Cu(2+) are highly photoreactive and can act as potential catalysts giving rise to oxidative radicals such as O2(-) , which initiate the transformation of PAHs. The present work provides valuable insights into understanding the transformation and fate of PAHs in the natural soil environment and sheds light on the development of technologies for contaminated land remediation. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Antisense oligodeoxynucleotide inhibition of a swelling-activated cation channel in osteoblast-like osteosarcoma cells

    NASA Technical Reports Server (NTRS)

    Duncan, R. L.; Kizer, N.; Barry, E. L.; Friedman, P. A.; Hruska, K. A.

    1996-01-01

    By patch-clamp analysis, we have shown that chronic, intermittent mechanical strain (CMS) increases the activity of stretch-activated cation channels of osteoblast-like UMR-106.01 cells. CMS also produces a swelling-activated whole-cell conductance (Gm) regulated by varying strain levels. We questioned whether the swelling-activated conductance was produced by stretch-activated cation channel activity. We have identified a gene involved in the increase in conductance by using antisense oligodeoxynucleotides (ODN) derived from the alpha 1-subunit genes of calcium channels found in UMR-106.01 cells (alpha1S, alpha1C, and alpha1D). We demonstrate that alpha 1C antisense ODNs abolish the increase in Gm in response to hypotonic swelling following CMS. Antisense ODNs to alpha1S and alpha1D, sense ODNs to alpha1C, and sham permeabilization had no effect on the conductance increase. In addition, during cell-attached patch-clamp studies, antisense ODNs to alpha1c completely blocked the swelling-activated and stretch-activated nonselective cation channel response to strain. Antisense ODNs to alpha1S treatment produced no effect on either swelling-activated or stretch-activated cation channel activity. There were differences in the stretch-activated and swelling-activated cation channel activity, but whether they represent different channels could not be determined from our data. Our data indicate that the alpha1C gene product is involved in the Gm and the activation of the swelling-activated cation channels induced by CMS. The possibility that swelling-activated cation channel genes are members of the calcium channel superfamily exists, but if alpha1c is not the swelling-activated cation channel itself, then its expression is required for induction of swelling-activated cation channel activity by CMS.

  4. The effect of various electrolyte cations on electrochemical performance of polypyrrole/RGO based supercapacitors.

    PubMed

    Zhu, Jianbo; Xu, Youlong; Wang, Jie; Lin, Jun; Sun, Xiaofei; Mao, Shengchun

    2015-11-21

    In this work, polypyrrole/graphene doped by p-toluenesulfonic is prepared as an active material for supercapacitors, and its capacitance performance is investigated in various aqueous electrolytes including HCl, LiCl, NaCl, and KCl with a concentration of 3 M, respectively. A rising trend of capacitance is observed according to the cationic mobility (Li(+) < Na(+) < K(+) < H(+)), which is due to its effect on the ionic conductivity, efficient ion/charge diffusion/exchange and relaxation time. On the other hand, long-term cycling stability is in the following order: KCl < NaCl < LiCl < HCl, corresponding to the decreasing tendency of cation size (K(+) > Na(+) > Li(+) > H(+)). The reason can be attributed to the fact that the insertion/de-insertion of large size cation brings a significant doping level decrease and an over-oxidation increase during the charging-discharging cycles. Hence, we not only obtain good capacitance performance (280.3 F g(-1) at 5 mV s(-1)), superior rate capability (225.8 F g(-1) at 500 mV s(-1)) and high cycling stability (92.0% capacitance retention after 10,000 cycles at 1 A g(-1)) by employing 3 M HCl as an electrolyte, but also reveal that the electrolyte cations have a significant effect on the supercapacitors' electrochemical performance.

  5. Studies on ocular and parenteral application potentials of azithromycin- loaded anionic, cationic and neutral-charged emulsions.

    PubMed

    Tamilvanan, Shunmugaperumal; Khanum, Ramona; Senthilkumar, Sudalimuthu Ramachandran; Muthuraman, Marimuthu; Rajasekharan, Thenrajan

    2013-10-01

    Ocular and parenteral application potentials of azithromycin-containing, non-phospholipid-based cationic nanosized emulsion in comparison to the phospholipid-based anionic and neutral-charged nanosized emulsions were investigated. Various physical, chemical, nonclinical toxicity and antimicrobial activity studies (mean droplet diameter, surface charge, creaming index, entrapment efficiency, accelerated, long-term and freeze-thaw cycling stabilities, TLC study, modified hen's egg chorioallantoic membrane (HET-CAM) test, in vitro hemolysis test, in vitro and in vivo myotoxicity, and in vitro antimicrobial activity) were conducted for assessing the potentials of these three types of emulsions. Following autoclave sterilization, all of these emulsions exhibited a nanometer range mean particle diameter (200 ± 29 to 434 ± 13 nm). While the anionic and cationic emulsions did show high negative (-34.2 ± 1.23 mV) and positive zeta potential (42.6 ± 1.45 mV) values, the neutral-charged emulsion did not. Even with 5 freeze-thaw cycles, the cationic emulsion remained stable whereas other two emulsions underwent phase-separation. The hen's egg chorioallantoic membrane test revealed an irritation score value that was higher for the anionic emulsion than for cationic or neutral-charged emulsion. A significantly higher % hemolysis value was also noticed for the anionic emulsion when compared to the % hemolysis value of cationic emulsion (ANOVA, P ‹ 0.05). However, all of the emulsions showed a lesser intracellular creatine kinase (CK) release/plasma CK level in comparison to the positive control (phenytoin) indicating their lesser myotoxicity at the injection site . When compared to anionic and neutral-charged emulsions, the possible controlled drug release from cationic emulsion delayed the in vitro antimicrobial action against H.influenzae and S.pneumoniae.

  6. Misfit strain driven cation inter-diffusion across an epitaxial multiferroic thin film interface

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

    Sankara Rama Krishnan, P. S.; Munroe, Paul; Nagarajan, V.

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

  7. Cation and anion sequences in dark-adapted Balanus photoreceptor

    PubMed Central

    1977-01-01

    Anion and cation permeabilities in dark-adapted Balanus photoreceptors were determined by comparing changes in the membrane potential in response to replacement of the dominant anion (Cl-) or cation (Na+) by test anions or cations in the superfusing solution. The anion permeability sequence obtained was PI greater than PSO4 greater than PBr greater than PCl greater than Pisethionate greater than Pmethanesulfonate. Gluconate, glucuronate, and glutamate generally appeared more permeable and propionate less permeable than Cl-. The alkali-metal cation permeability sequence obtained was PK greater than PRb greater than PCx greater than PNa approximately PLi. This corresponds to Eisenman's IV which is the same sequencethat has been obtained for other classes of nerve cells in the resting state. The values obtained for the permeability ratios of the alkali-metal cations are considered to be minimal. The membrane conductance measured by passing inward current pulses in the different test cations followed the sequence, GK greater than GRb greater than GCs greater than GNa greater than GLi. The conductance ratios obtained for a full substitution of the test cation agreed quite well with permeability ratios for all the alkali-metal cations except K+ which was generally higher. PMID:199688

  8. Equilibrium Acidities and Homolytic Bond Dissociation Enthalpies of the Acidic C-H Bonds in P-(Para-substituted benzyl)triphenylphosphonium Cations and Related Cations.

    PubMed

    Zhang, Xian-Man; Fry, Albert J.; Bordwell, Frederick G.

    1996-06-14

    Equilibrium acidities (pK(HA)) of six P-(para-substituted benzyl)triphenylphosphonium (p-GC(6)H(4)CH(2)PPh(3)(+)) cations, P-allyltriphenylphosphonium cation, P-cinnamyltriphenylphosphonium cation, and As-(p-cyanobenzyl)triphenylarsonium cation, together with the oxidation potentials [E(ox)(A(-))] of their conjugate anions (ylides) have been measured in dimethyl sulfoxide (DMSO) solution. The acidifying effects of the alpha-triphenylphosphonium groups on the acidic C-H bonds in toluene and propene were found to be ca 25 pK(HA) units (34 kcal/mol). Introduction of an electron-withdrawing group such as 4-NO(2), 4-CN, or 4-Br into the para position of the benzyl ring in p-GC(6)H(4)CH(2)PPh(3)(+) cations resulted in an additional acidity increase, but introduction of the 4-OEt electron-donating group decreases the acidity. The equilibrium acidities of p-GC(6)H(4)CH(2)PPh(3)(+) cations were nicely linearly correlated with the Hammett sigma(-) constants of the substituents (G) with a slope of 4.78 pK(HA) units (R(2) = 0.992) (Figure 1). Reversible oxidation potentials of the P-(para-substituted benzyl)triphenylphosphonium ylides were obtained by fast scan cyclic voltammetry. The homolytic bond dissociation enthalpies (BDEs) of the acidic C-H bonds in these cations, estimated by combining their equilibrium acidities with the oxidation potentials of their corresponding conjugate anions, showed that the alpha-Ph(3)P(+) groups have negligible stabilizing or destabilizing effects on the adjacent radicals. The equilibrium acidity of As-(p-cyanobenzyl)triphenylarsonium cation is 4 pK(HA) units weaker than that of P-(p-cyanobenzyl)triphenylphosphonium cation, but the BDE of the acidic C-H bond in As-(p-cyanobenzyl)triphenylarsonium cation is ca 2 kcal/mol higher than that in P-(p-cyanobenzyl)triphenylphosphonium cation.

  9. Distinguishing Biologically Relevant Hexoses by Water Adduction to the Lithium-Cationized Molecule.

    PubMed

    Campbell, Matthew T; Chen, Dazhe; Wallbillich, Nicholas J; Glish, Gary L

    2017-10-03

    A method to distinguish the four most common biologically relevant underivatized hexoses, d-glucose, d-galactose, d-mannose, and d-fructose, using only mass spectrometry with no prior separation/derivatization step has been developed. Electrospray of a solution containing hexose and a lithium salt generates [Hexose+Li] + . The lithium-cationized hexoses adduct water in a quadrupole ion trap. The rate of this water adduction reaction can be used to distinguish the four hexoses. Additionally, for each hexose, multiple lithiation sites are possible, allowing for multiple structures of [Hexose+Li] + . Electrospray produces at least one structure that reacts with water and at least one that does not. The ratio of unreactive lithium-cationized hexose to total lithium-cationized hexose is unique for the four hexoses studied, providing a second method for distinguishing the isomers. Use of the water adduction reaction rate or the unreactive ratio provides two separate methods for confidently (p ≤ 0.02) distinguishing the most common biologically relevant hexoses using only femtomoles of hexose. Additionally, binary mixtures of glucose and fructose were studied. A calibration curve was created by measuring the reaction rate of various samples with different ratios of fructose and glucose. The calibration curve was used to accurately measure the percentage of fructose in three samples of high fructose corn syrup (<4% error).

  10. Potassium Niobate Nanolamina: A Promising Adsorbent for Entrapment of Radioactive Cations from Water

    PubMed Central

    Sun, Jin; Yang, Dongjiang; Sun, Cuihua; Liu, Long; Yang, Shuanglei; (Alec) Jia, Yi; Cai, Rongsheng; Yao, Xiangdong

    2014-01-01

    Processing and managing radioactive waste is a great challenge worldwide as it is extremely difficult and costly; the radioactive species, cations or anions, leaked into the environment are a serious threat to the health of present and future generations. We report layered potassium niobate (K4Nb6O17) nanolamina as adsorbent to remove toxic Sr2+, Ba2+ and Cs+ cations from wastewater. The results show that K4Nb6O17 nanolamina can permanently confine the toxic cations within the interlayer spacing via a considerable deformation of the metastable layered structure during the ion exchange process. At the same time, the nanolaminar adsorbent exhibits prompt adsorption kinetics, high adsorption capacity and selectivity, and superior acid resistance. These merits make it be a promising material as ion exchanger for the removal of radioactive cations from wastewater. PMID:25472721

  11. Potassium niobate nanolamina: a promising adsorbent for entrapment of radioactive cations from water.

    PubMed

    Sun, Jin; Yang, Dongjiang; Sun, Cuihua; Liu, Long; Yang, Shuanglei; Alec Jia, Yi; Cai, Rongsheng; Yao, Xiangdong

    2014-12-04

    Processing and managing radioactive waste is a great challenge worldwide as it is extremely difficult and costly; the radioactive species, cations or anions, leaked into the environment are a serious threat to the health of present and future generations. We report layered potassium niobate (K4Nb6O17) nanolamina as adsorbent to remove toxic Sr(2+), Ba(2+) and Cs(+) cations from wastewater. The results show that K4Nb6O17 nanolamina can permanently confine the toxic cations within the interlayer spacing via a considerable deformation of the metastable layered structure during the ion exchange process. At the same time, the nanolaminar adsorbent exhibits prompt adsorption kinetics, high adsorption capacity and selectivity, and superior acid resistance. These merits make it be a promising material as ion exchanger for the removal of radioactive cations from wastewater.

  12. Does Cation Size Affect Occupancy and Electrostatic Screening of the Nucleic Acid Ion Atmosphere?

    PubMed Central

    2016-01-01

    Electrostatics are central to all aspects of nucleic acid behavior, including their folding, condensation, and binding to other molecules, and the energetics of these processes are profoundly influenced by the ion atmosphere that surrounds nucleic acids. Given the highly complex and dynamic nature of the ion atmosphere, understanding its properties and effects will require synergy between computational modeling and experiment. Prior computational models and experiments suggest that cation occupancy in the ion atmosphere depends on the size of the cation. However, the computational models have not been independently tested, and the experimentally observed effects were small. Here, we evaluate a computational model of ion size effects by experimentally testing a blind prediction made from that model, and we present additional experimental results that extend our understanding of the ion atmosphere. Giambasu et al. developed and implemented a three-dimensional reference interaction site (3D-RISM) model for monovalent cations surrounding DNA and RNA helices, and this model predicts that Na+ would outcompete Cs+ by 1.8–2.1-fold; i.e., with Cs+ in 2-fold excess of Na+ the ion atmosphere would contain an equal number of each cation (Nucleic Acids Res.2015, 43, 8405). However, our ion counting experiments indicate that there is no significant preference for Na+ over Cs+. There is an ∼25% preferential occupancy of Li+ over larger cations in the ion atmosphere but, counter to general expectations from existing models, no size dependence for the other alkali metal ions. Further, we followed the folding of the P4–P6 RNA and showed that differences in folding with different alkali metal ions observed at high concentration arise from cation–anion interactions and not cation size effects. Overall, our results provide a critical test of a computational prediction, fundamental information about ion atmosphere properties, and parameters that will aid in the development of

  13. [2.2.2]Paracyclophane as a receptor for the cesium cation in the gas phase

    NASA Astrophysics Data System (ADS)

    Makrlík, Emanuel; Sýkora, David; Böhm, Stanislav; Vaňura, Petr

    2017-10-01

    By using electrospray ionisation mass spectrometry, it was proven experimentally that the cesium cation (Cs+) forms with [2.2.2]paracyclophane (C24H24) the cationic complex [Cs(C24H24)]+. Further, applying quantum chemical calculations, the most probable structure of the [Cs(C24H24)]+ complex was derived. In the resulting complex with a symmetry very close to C3, the 'central' cation Cs+, fully located in the cavity of the parent [2.2.2]paracyclophane ligand, is bound to all three benzene rings of [2.2.2]paracyclophane via cation-π interaction. Finally, the interaction energy, E(int), of the considered cation-π complex [Cs(C24H24)]+ was found to be -73.2 kJ/mol, confirming the formation of this fascinating complex species as well. This means that [2.2.2]paracyclophane can be considered as a receptor for the Cs+ cation in the gas phase.

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

    PubMed

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

    2017-06-15

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

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

    PubMed

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

    2011-01-01

    TRPV6 belongs to the vanilloid family of the transient receptor potential channel (TRP) superfamily. This calcium-selective channel is highly expressed in the duodenum and the placenta, being responsible for calcium absorption in the body and fetus. Previous observations have suggested that TRPV6 is not only permeable to calcium but also to other divalent cations in epithelial tissues. In this study, we tested whether TRPV6 is indeed also permeable to cations such as zinc and cadmium. We found that the basal intracellular calcium concentration was higher in HEK293 cells transfected with hTRPV6 than in non-transfected cells, and that this difference almost disappeared in nominally calcium-free solution. Live cell imaging experiments with Fura-2 and NewPort Green DCF showed that overexpression of human TRPV6 increased the permeability for Ca(2+), Ba(2+), Sr(2+), Mn(2+), Zn(2+), Cd(2+), and interestingly also for La(3+) and Gd(3+). These results were confirmed using the patch clamp technique. (45)Ca uptake experiments showed that cadmium, lanthanum and gadolinium were also highly efficient inhibitors of TRPV6-mediated calcium influx at higher micromolar concentrations. Our results suggest that TRPV6 is not only involved in calcium transport but also in the transport of other divalent cations, including heavy metal ions, which may have toxicological implications. Copyright © 2010 Elsevier Ltd. All rights reserved.

  16. Dopant-Site Determination in Y- and Sc-Doped (Ba0.5Sr0.5)(Co0.8Fe0.2)O3-δ by Atom Location by Channeling Enhanced Microanalysis and the Role of Dopant Site on Secondary Phase Formation.

    PubMed

    Meffert, Matthias; Störmer, Heike; Gerthsen, Dagmar

    2016-02-01

    (Ba0.5Sr0.5)(Co0.8Fe0.2)O3-δ (BSCF) is a promising material with mixed ionic and electronic conductivity which is considered for oxygen separation membranes. Selective improvement of material properties, e.g. oxygen diffusivity or suppression of secondary phase formation, can be achieved by B-site doping. This study is concerned with the formation of Co-oxide precipitates in undoped BSCF at typical homogenization temperatures of 1,000°C, which act as undesirable nucleation sites for other secondary phases in the application-relevant temperature range. Y-doping successfully suppresses Co-oxide formation, whereas only minor improvements are achieved by Sc-doping. To understand the reason for the different behavior of Y and Sc, the lattice sites of dopant cations in BSCF were experimentally determined in this work. Energy-dispersive X-ray spectroscopy in a transmission electron microscope was applied to locate dopant sites exploiting the atom location by channeling enhanced microanalysis technique. It is shown that Sc exclusively occupies B-cation sites, whereas Y is detected on A- and B-cation sites in Y-doped BSCF, although solely B-site doping was intended. A model is presented for the suppression of Co-oxide formation in Y-doped BSCF based on Y double-site occupancy.

  17. Amylose-Based Cationic Star Polymers for siRNA Delivery.

    PubMed

    Nishimura, Tomoki; Umezaki, Kaori; Mukai, Sada-atsu; Sawada, Shin-ichi; Akiyoshi, Kazunari

    2015-01-01

    A new siRNA delivery system using a cationic glyco-star polymer is described. Spermine-modified 8-arm amylose star polymer (with a degree of polymerization of approximately 60 per arm) was synthesized by chemoenzymatic methods. The cationic star polymer effectively bound to siRNA and formed spherical complexes with an average hydrodynamic diameter of 230 nm. The cationic 8-arm star polymer complexes showed superior cellular uptake characteristics and higher gene silencing effects than a cationic 1-arm polymer. These results suggest that amylose-based star polymers are a promising nanoplatform for glycobiomaterials.

  18. Mechanistic insights into allosteric regulation of the A 2A adenosine G protein-coupled receptor by physiological cations

    DOE PAGES

    Ye, Libin; Neale, Chris Andrew; Sljoka, Adnan; ...

    2018-04-10

    Cations play key roles in regulating G-protein-coupled receptors (GPCRs), although their mechanisms are poorly understood. Here, 19F NMR is used to delineate the effects of cations on functional states of the adenosine A 2A GPCR. While Na + reinforces an inactive ensemble and a partial-agonist stabilized state, Ca 2+ and Mg 2+ shift the equilibrium toward active states. Positive allosteric effects of divalent cations are more pronounced with agonist and a G-protein-derived peptide. In cell membranes, divalent cations enhance both the affinity and fraction of the high affinity agonist-bound state. Molecular dynamics simulations suggest high concentrations of divalent cations bridgemore » specific extracellular acidic residues, bringing TM5 and TM6 together at the extracellular surface and allosterically driving open the G-protein-binding cleft as shown by rigidity-transmission allostery theory. Lastly, an understanding of cation allostery should enable the design of allosteric agents and enhance our understanding of GPCR regulation in the cellular milieu.« less

  19. Mechanistic insights into allosteric regulation of the A 2A adenosine G protein-coupled receptor by physiological cations

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

    Ye, Libin; Neale, Chris Andrew; Sljoka, Adnan

    Cations play key roles in regulating G-protein-coupled receptors (GPCRs), although their mechanisms are poorly understood. Here, 19F NMR is used to delineate the effects of cations on functional states of the adenosine A 2A GPCR. While Na + reinforces an inactive ensemble and a partial-agonist stabilized state, Ca 2+ and Mg 2+ shift the equilibrium toward active states. Positive allosteric effects of divalent cations are more pronounced with agonist and a G-protein-derived peptide. In cell membranes, divalent cations enhance both the affinity and fraction of the high affinity agonist-bound state. Molecular dynamics simulations suggest high concentrations of divalent cations bridgemore » specific extracellular acidic residues, bringing TM5 and TM6 together at the extracellular surface and allosterically driving open the G-protein-binding cleft as shown by rigidity-transmission allostery theory. Lastly, an understanding of cation allostery should enable the design of allosteric agents and enhance our understanding of GPCR regulation in the cellular milieu.« less

  20. Unusual pi-donating effects of pi-accepting substituents on the stabilities of benzylic cations: a theoretical study.

    PubMed

    Kim, Chang Kon; Han, In Suk; Ryu, Wang Sun; Lee, Hai Whang; Lee, Bon-Su; Kim, Chan Kyung

    2006-02-23

    The pi-donating effects of pi-accepting X-substituents in substituted benzylic cations, X-C(6)H(5)-CHR(+) where R = CF(3), H and OCH(3), and X = p-NH(2), p-OCH(3), p-CH(3), H, p-F, p-Cl, p-CHO, m-CN, p-CN, m-NO(2) or p-NO(2), have been studied theoretically by using isodesmic hydride transfer reactions at various levels of theory. It might be difficult to determine the pi-donating effects of pi-acceptors using the simple Hammett-type linear equation, because it is not sensitive enough to include small pi-donating effects. Therefore, this effect was estimated using the NBO deletion energy (DeltaE(D)) of the second-order charge-transfer interaction (DeltaE(ct)) between the pi-orbitals (or lone pair orbitals) of the X-substituent and the pi-orbitals of phenyl ring. The extents of pi-donating effects increased in the order X = p-NO(2) < p-CHO < p-CN < p-Cl for both neutral and cationic species, and these effects were found to be more important for para- than for meta-substituents. Moreover, this could represent a general trend for pi-donation by pi-acceptors. On the other hand, the effects of R-substituents on this pi-donating effect were found to be in the order R = OCH(3) < H congruent with CF(3), as predicted by natural resonance theory (NRT) analyses.

  1. Membrane stress increases cation permeability in red cells.

    PubMed

    Johnson, R M

    1994-11-01

    The human red cell is known to increase its cation permeability when deformed by mechanical forces. Light-scattering measurements were used to quantitate the cell deformation, as ellipticity under shear. Permeability to sodium and potassium was not proportional to the cell deformation. An ellipticity of 0.75 was required to increase the permeability of the membrane to cations, and flux thereafter increased rapidly as the limits of cell extension were reached. Induction of membrane curvature by chemical agents also did not increase cation permeability. These results indicate that membrane deformation per se does not increase permeability, and that membrane tension is the effector for increased cation permeability. This may be relevant to some cation permeabilities observed by patch clamping.

  2. New cationic vesicles prepared with double chain surfactants from arginine: Role of the hydrophobic group on the antimicrobial activity and cytotoxicity.

    PubMed

    Pinazo, A; Petrizelli, V; Bustelo, M; Pons, R; Vinardell, M P; Mitjans, M; Manresa, A; Perez, L

    2016-05-01

    Cationic double chain surfactants have attracted much interest because they can give rise to cationic vesicles that can be used in biomedical applications. Using a simple and economical synthetic approach, we have synthesized four double-chain surfactants with different alkyl chain lengths (LANHCx). The critical aggregation concentration of the double chain surfactants is at least one order of magnitude lower than the CMC of their corresponding single-chain LAM and the solutions prepared with the LANHCx contain stable cationic vesicles. Encouragingly, these new arginine derivatives show very low haemolytic activity and weaker cytotoxic effects than conventional dialkyl dimethyl ammonium surfactants. In addition, the surfactant with the shortest alkyl chain exhibits good antimicrobial activity against Gram-positive bacteria. The results show that a rational design applied to cationic double chain surfactants might serve as a promising strategy for the development of safe cationic vesicular systems. Copyright © 2016 Elsevier B.V. All rights reserved.

  3. The tert-butyl cation on zeolite Y: A theoretical and experimental study

    NASA Astrophysics Data System (ADS)

    Rosenbach, Nilton, Jr.; dos Santos, Alex P. A.; Franco, Marcelo; Mota, Claudio J. A.

    2010-01-01

    The structure and energy of the tert-butyl cation on zeolite Y were calculated at ONIOM(MP2(FULL)/6-31G( d, p):MNDO) level. The results indicated that the tert-butyl cation is a minimum and lies between 40 and 51 kJ mol -1 above in energy to the tert-butoxide, depending on the level of calculation. Both species are stabilized through hydrogen bonding interactions with the framework oxygen atoms. Experimental data of nucleophilic substitution of tert-butylchloride and bromide over NaY impregnated with NaCl or NaBr give additional support for the formation of the tert-butyl cation as a discrete intermediate on zeolite Y, in agreement with the calculations.

  4. Cationic polymer brush-modified cellulose nanocrystals for high-affinity virus binding

    NASA Astrophysics Data System (ADS)

    Rosilo, Henna; McKee, Jason R.; Kontturi, Eero; Koho, Tiia; Hytönen, Vesa P.; Ikkala, Olli; Kostiainen, Mauri A.

    2014-09-01

    Surfaces capable of high-affinity binding of biomolecules are required in several biotechnological applications, such as purification, transfection, and sensing. Therein, the rod-shaped, colloidal cellulose nanocrystals (CNCs) are appealing due to their large surface area available for functionalization. In order to exploit electrostatic binding, their intrinsically anionic surfaces have to be cationized as biological supramolecules are predominantly anionic. Here we present a facile way to prepare cationic CNCs by surface-initiated atom-transfer radical polymerization of poly(N,N-dimethylaminoethyl methacrylate) and subsequent quaternization of the polymer pendant amino groups. The cationic polymer brush-modified CNCs maintained excellent dispersibility and colloidal stability in water and showed a ζ-potential of +38 mV. Dynamic light scattering and electron microscopy showed that the modified CNCs electrostatically bind cowpea chlorotic mottle virus and norovirus-like particles with high affinity. Addition of only a few weight percent of the modified CNCs in water dispersions sufficed to fully bind the virus capsids to form micrometer-sized assemblies. This enabled the concentration and extraction of the virus particles from solution by low-speed centrifugation. These results show the feasibility of the modified CNCs in virus binding and concentrating, and pave the way for their use as transduction enhancers for viral delivery applications.Surfaces capable of high-affinity binding of biomolecules are required in several biotechnological applications, such as purification, transfection, and sensing. Therein, the rod-shaped, colloidal cellulose nanocrystals (CNCs) are appealing due to their large surface area available for functionalization. In order to exploit electrostatic binding, their intrinsically anionic surfaces have to be cationized as biological supramolecules are predominantly anionic. Here we present a facile way to prepare cationic CNCs by surface

  5. 77 FR 58867 - Public Land Order No. 7799; Withdrawal of Public Land for the Rock Springs Administrative Site...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-09-24

    ...] Public Land Order No. 7799; Withdrawal of Public Land for the Rock Springs Administrative Site Addition..., including the United States mining laws, for a period of 20 years to protect the Rock Springs Administrative... improvements associated with development and maintenance of the Rock Springs Administrative Site addition. The...

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

    PubMed

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

    2011-12-01

    A combination of explicit solvent molecular dynamics simulation (30 simulations reaching 4 µs in total), hybrid quantum mechanics/molecular mechanics approach and isothermal titration calorimetry was used to investigate the atomistic picture of ion binding to 15-mer thrombin-binding quadruplex DNA (G-DNA) aptamer. Binding of ions to G-DNA is complex multiple pathway process, which is strongly affected by the type of the cation. The individual ion-binding events are substantially modulated by the connecting loops of the aptamer, which play several roles. They stabilize the molecule during time periods when the bound ions are not present, they modulate the route of the ion into the stem and they also stabilize the internal ions by closing the gates through which the ions enter the quadruplex. Using our extensive simulations, we for the first time observed full spontaneous exchange of internal cation between quadruplex molecule and bulk solvent at atomistic resolution. The simulation suggests that expulsion of the internally bound ion is correlated with initial binding of the incoming ion. The incoming ion then readily replaces the bound ion while minimizing any destabilization of the solute molecule during the exchange. © The Author(s) 2011. Published by Oxford University Press.

  7. Structural charge site influence on the interlayer hydration of expandable three-sheet clay minerals

    USGS Publications Warehouse

    Kerns, Raymond L.; Mankin, Charles J.

    1968-01-01

    Previous investigations have demonstrated the influences of interlayer cation composition, relative humidity, temperature, and magnitude of interlayer surface charge on the interlayer hydration of montmorillonites and vermiculites. It has been suggested that the sites of layer charge deficiencies may also have an influence upon the amount of hydration that can take place in the interlayers of expandable clay minerals. If the interlayer cation-to-layer bonds are considered as ideally electrostatic, the magnitude of the forces resisting expansion may be expressed as a form of Coulomb's law. If this effect is significant, expandable structures in which the charge-deficiency sites are predominantly in the tetrahedral sheet should have less pronounced swelling properties than should structures possessing charge deficiencies located primarily in the octahedral sheet.Three samples that differed in location of layer charge sites were selected for study. An important selection criterion was a non-correlation between tetrahedral charge sites and high surface-charge density, and between octahedral charge sites and low surface-charge density.The effects of differences in interlayer cation composition were eliminated by saturating portions of each sample with the same cations. Equilibrium (001) d values at controlled constant humidities were used as a measure of the relative degree of interlayer hydration.Although no correlation could be made between the degree of interlayer hydration and total surface-charge density, the investigation does not eliminate total surface-charge density as being significant to the swelling properties of three-sheet clay-mineral structures. The results do indicate a correlation between more intense expandability and predominance of charge deficiencies in the octahedral sheet. Conversely, less intense swelling behavior is associated with predominantly tetrahedral charge deficiencies.

  8. Infrared Spectroscopy of Matrix-Isolated Polycyclic Aromatic Hydrocarbon Cations. 3; The Polyacenes Anthracene, Tetracence, and Pentacene

    NASA Technical Reports Server (NTRS)

    Hudgins, D. M.; Allamandola, L. J.

    1995-01-01

    Gaseous, ionized polycyclic aromatic hydrocarbons (PAHS) are thought to be responsible for a very common family of interstellar infrared emission bands. Unfortunately, very little infrared spectroscopic data are available on ionized PAHS. Here we present the near- and mid-infrared spectra of the polyacene cations anthracene, tetracene, and pentacene. We also report the vibrational frequencies and relative intensities of the pentacene anion. The cation bands corresponding to the CC modes are typically about 10-20 times more intense than those of the CH out-of-plane bending vibrations. For the cations the CC stretching and CH in-plane bending modes give rise to bands which are an order of magnitude stronger than for the neutral species, and the CH out-of-plane bends produce bands which are 3-20 times weaker than in the neutral species. This behavior is similar to that found for most other PAH cations. The most intense PAH cation bands fall within the envelopes of the most intense interstellar features. The strongest absorptions in the polyacenes anthracene, tetracene, and pentacene tend to group around 1400/cm (between about 1340 and 1500/cm) and near 1180/cm, regions of only moderate interstellar emission. These very strong polyacene bands tend to fall in gaps in the spectra of the other PAH cations studied to date suggesting that while PAHs with polyacene structures may contribute to specific regions of the interstellar emission spectra, they are not dominant members of the interstellar PAH family.

  9. Infrared Spectroscopy of Matrix-Isolated Polycyclic Aromatic Hydrocarbon Cations. 3. The Polyacenes Anthracene, Tetracene, and Pentacene

    NASA Technical Reports Server (NTRS)

    Hudgins, D. M.; Allamandola, L. J.

    1995-01-01

    Gaseous, ionized Polycyclic Aromatic Hydrocarbons (PAH's) are thought to be responsible for a very common family of interstellar infrared emission bands. Unfortunately, very little infrared spectroscopic data are available on ionized PAH's. Here we present the near- and mid-infrared spectra of the polyacene cations anthracene, tetracene, and pentacene. We also report the vibrational frequencies and relative intensities of the pentacene anion. The cation bands corresponding to the CC modes are typically about 10-20 times more intense than those of the CH out-of-plane bending vibrations. For the cations the CC stretching and CH in-plane bending modes give rise to bands which are an order of magnitude stronger than for the neutral species, and the CH out-of-plane bends produce bands which are 3-20 times weaker than in the neutral species. This behavior is similar to that found for most other PAH cations. The most intense PAH cation bands fall within the envelopes of the most intense interstellar features. The strongest absorptions in the polyacenes anthracene, tetracene, and pentacene tend to group around 1400 / cm (between about 1340 and 1500 / cm) and near 1180 /cm, regions of only moderate interstellar emission. These very strong polyacene bands tend to fall in gaps in the spectra of the other PAH cations studied to date suggesting that while PAHs with polyacene structures may contribute to specific regions of the interstellar emission spectra, they are not dominant members of the interstellar PAH family.

  10. Closed-Shell Polycyclic Aromatic Hydrocarbon Cations: A New Category of Interstellar Polycyclic Aromatic Hydrocarbons

    NASA Technical Reports Server (NTRS)

    Hudgins, Douglas M.; Bauschlicher, Charles W., Jr.; Allamandola, Louis J.; DeVincenzi, Donald (Technical Monitor)

    2001-01-01

    Density functional theory has been employed to calculate the harmonic frequencies and intensities of a range of polycyclic aromatic hydrocarbon (PAH) cations that explore both size and electronic structure effects of the infrared spectroscopic properties of these species. The sample extends the size range of PAH species considered to more than 50 carbon atoms and includes several representatives from each of two heretofore unexplored categories of PAH cations: (1) fully benzenoid PAH cations whose carbon skeleton is composed of an odd number of carbon atoms (C(sub odd) PAHs); and (2) protonated PAH cations (HPAH+). Unlike the radical electronic structures of the PAH cations that have been the subject of previous theoretical and experimental work, the species in these two classes have a closed-shell electronic configuration. The calculated spectra of circumcoronene, C54H18 in both neutral and (radical) cationic form are also reported and compared with those of the other species. Overall, the C(sub odd) PAHs spectra are dominated by strong CC stretching modes near 1600 cm(exp -1) and display spectra that are remarkably insensitive to molecular size. The HPAH+ species evince a more complex spectrum consistent with the added contributions of aliphatic modes and their generally lower symmetry. Finally, for both classes of closed-shell cations, the intensity of the aromatic CH stretching modes is found to increase with molecular size far out of proportion with the number of CH groups, approaching a value more typical of neutral PAHs for the largest species studied.

  11. The role of multivalent metal cations and organic complexing agents in bitumen-mineral interactions in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Gan, Weibing

    A systematic investigation was carried out to study the interactions between bitumen (or hexadecane) and minerals (quartz, kaolinite and illite) in aqueous solutions containing multivalent metal cations Ca2+, Mg2+ and Fe2+/Fe3+, in the absence and presence of organic complexing agents (oxalic acid, EDTA and citric acid). A range of experimental techniques, including coagulation measurement, visualization of bitumen-mineral attachment, metal ion adsorption measurement, zeta potential measurement, Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopic analyses, were employed in the investigation. Free energy changes of adsorption of metal cations on the minerals and bitumen were evaluated using the James & Healy thermodynamic model. Total interaction energies between the minerals and bitumen were calculated using classical DLVO theory. It was observed that while the tested minerals showed varying degrees of mutual-coagulation with bitumen (or hexadecane), the presence of the multivalent metal cations could prominently increase the mutual coagulation. It was also found that such enhancement of the mutual coagulation was only significant when the metal cations formed first-order hydroxyl complexes (such as CaOH +, MgOH+, etc.) or metal hydroxides (such as Fe(OH) 3, Mg(OH)2, etc.). Therefore, the increase of the bitumen-mineral mutual coagulation by the metal cations was strongly pH dependent. Organic complexing agents (oxalic acid, citric acid and EDTA) used in this study, citric acid in particular, significantly reduced or virtually eliminated the mutual coagulation between bitumen (or hexadecane) and minerals caused by metal cations Ca2+, Mg2+, Fe 2+ and Fe3+. Due to its ability to substantially lower the mutual coagulation between bitumen and mineral particles, citric acid was found the most effective in improving bitumen-mineral liberation in solutions containing the multivalent metal cations at pH 8--10. In small scale flotation experiments

  12. Cation-Pi Interaction: A Key Force for Sorption of Fluoroquinolone Antibiotics on Pyrogenic Carbonaceous Materials.

    PubMed

    Zhao, Qing; Zhang, Siyu; Zhang, Xuejiao; Lei, Lei; Ma, Wei; Ma, Chuanxin; Song, Lei; Chen, Jingwen; Pan, Bo; Xing, Baoshan

    2017-12-05

    Cation-pi attraction is a major force that determines macromolecular structures and drug-receptor interactions. However, the role of the cation-pi interaction in sorption of fluoroquinolone antibiotics by pyrogenic carbonaceous materials (PCMs) has not been addressed. We studied sorption of ciprofloxacin (CIP) on graphite to quantify the contribution of the cation-pi interaction. Through competition experiments, the decreased amount of sorbed CIP by sequential treatment with hexadecane, phenanthrene and benzylamine represents the contribution of hydrophobic, pi-pi and cation-pi interactions, respectively. Benzylamine competed more strongly with CIP than n-hexadecane and phenanthrene, indicating that cation-pi is a major force. Cation-pi interactions accounted for up to 72.6% of the total sorption at an initial CIP concentration of 0.000015 mmol/L. Importantly, species transformation (CIP(0) captures H + from water to form CIP(+1)) induced by cation-pi interactions was verified both experimentally and theoretically and can be used to explain the environmental behavior of other fluoroquinolone antibiotics and biochemical processes of amino acids that interact with aromatic moieties. Because of the significant role of cation-pi interactions, CIP desorption increased up to 2.32 times when Na + increased from 0.01 mM to 0.45 mM, which is an environmentally relevant scenario at river estuaries. Hence, behaviors of fluoroquinolone antibiotics that are affected by ionic strength changes need to be carefully evaluated, especially in river estuaries.

  13. Molecular Dynamics Simulation of Resin Adsorption at Kaolinite Edge Sites: Effect of Surface Deprotonation on Interfacial Structure

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

    Zeitler, T. R.; Greathouse, J. A.; Cygan, R. T.

    Low-salinity water flooding, a method of enhanced oil recovery, consists of injecting low ionic strength fluids into an oil reservoir in order to detach oil from mineral surfaces in the underlying formation. Although highly successful in practice, the approach is not completely understood at the molecular scale. Molecular dynamics simulations have been used to investigate the effect of surface protonation on the adsorption of an anionic crude oil component on clay mineral edge surfaces. A set of interatomic potentials appropriate for edge simulations has been applied to the kaolinite (010) surface in contact with an aqueous nanopore. Decahydro-2-napthoic acid inmore » its deprotonated form (DHNA –) was used as a representative resin component of crude oil, with monovalent and divalent counterions, to test the observed trends in low-salinity water flooding experiments. Surface models include fully protonated (neutral) and deprotonated (negative) edge sites, which require implementation of a new deprotonation scheme. The surface adsorptive properties of the kaolinite edge under neutral and deprotonated conditions have been investigated for low and high DHNA – concentrations with Na + and Ca 2+ as counterions. The tendency of DHNA – ions to coordinate with divalent (Ca 2+) rather than monovalent (Na +) ions greatly influences adsorption tendencies of the anion. Additionally, the formation of net positively charged surface sites due to Ca 2+ at deprotonated sites results in increased DHNA – adsorption. Divalent cations such as Ca 2+ are able to efficiently bridge surface sites and organic anions. Replacing those cations with monovalent cations such as Na + diminishes the bridging mechanism, resulting in reduced adsorption of the organic species. As a result, a clear trend of decreased DHNA – adsorption is observed in the simulations as Ca 2+ is replaced by Na + for deprotonated surfaces, as would be expected for oil detachment from reservoir formations

  14. Molecular Dynamics Simulation of Resin Adsorption at Kaolinite Edge Sites: Effect of Surface Deprotonation on Interfacial Structure

    DOE PAGES

    Zeitler, T. R.; Greathouse, J. A.; Cygan, R. T.; ...

    2017-10-05

    Low-salinity water flooding, a method of enhanced oil recovery, consists of injecting low ionic strength fluids into an oil reservoir in order to detach oil from mineral surfaces in the underlying formation. Although highly successful in practice, the approach is not completely understood at the molecular scale. Molecular dynamics simulations have been used to investigate the effect of surface protonation on the adsorption of an anionic crude oil component on clay mineral edge surfaces. A set of interatomic potentials appropriate for edge simulations has been applied to the kaolinite (010) surface in contact with an aqueous nanopore. Decahydro-2-napthoic acid inmore » its deprotonated form (DHNA –) was used as a representative resin component of crude oil, with monovalent and divalent counterions, to test the observed trends in low-salinity water flooding experiments. Surface models include fully protonated (neutral) and deprotonated (negative) edge sites, which require implementation of a new deprotonation scheme. The surface adsorptive properties of the kaolinite edge under neutral and deprotonated conditions have been investigated for low and high DHNA – concentrations with Na + and Ca 2+ as counterions. The tendency of DHNA – ions to coordinate with divalent (Ca 2+) rather than monovalent (Na +) ions greatly influences adsorption tendencies of the anion. Additionally, the formation of net positively charged surface sites due to Ca 2+ at deprotonated sites results in increased DHNA – adsorption. Divalent cations such as Ca 2+ are able to efficiently bridge surface sites and organic anions. Replacing those cations with monovalent cations such as Na + diminishes the bridging mechanism, resulting in reduced adsorption of the organic species. As a result, a clear trend of decreased DHNA – adsorption is observed in the simulations as Ca 2+ is replaced by Na + for deprotonated surfaces, as would be expected for oil detachment from reservoir formations

  15. Amylose-Based Cationic Star Polymers for siRNA Delivery

    PubMed Central

    Nishimura, Tomoki; Umezaki, Kaori; Mukai, Sada-atsu; Sawada, Shin-ichi; Akiyoshi, Kazunari

    2015-01-01

    A new siRNA delivery system using a cationic glyco-star polymer is described. Spermine-modified 8-arm amylose star polymer (with a degree of polymerization of approximately 60 per arm) was synthesized by chemoenzymatic methods. The cationic star polymer effectively bound to siRNA and formed spherical complexes with an average hydrodynamic diameter of 230 nm. The cationic 8-arm star polymer complexes showed superior cellular uptake characteristics and higher gene silencing effects than a cationic 1-arm polymer. These results suggest that amylose-based star polymers are a promising nanoplatform for glycobiomaterials. PMID:26539548

  16. A Theoretical Investigation of the Infrared Spectroscopic Properties of Closed-Shell Polycyclic Aromatic Hydrocarbon Cations

    NASA Technical Reports Server (NTRS)

    Hudgins, Douglas M.; Bauschlicher, Charles W., Jr.; Allamandola, Louis J.; DeVincenzi, Donald L. (Technical Monitor)

    2000-01-01

    Density functional theory has been employed to calculate the harmonic frequencies and intensities of a range of PAH cations which explore both size and electronic structure effects on the infrared spectroscopic of these species. The sample extends the size range of PAH species considered to more than 50 carbon atoms and includes several representatives from each of two heretofore unexplored categories of PAH cations: (1) fully benzenoid PAH cations whose carbon skeleton is composed of an odd number of carbon atoms and (2) protonated PAH cations. Unlike the radical electronic structures of the PAH cations that have been the subject of previous theoretical and experimental work, the species in these two classes have a closed-shell electronic configuration. The calculated spectra of circumcoronene, C54H18, in both neutral and (radical) cationic form are also reported and compared to those of the other species. Closed-shell species are inherently less reactive than radical (or open-shell) cations and are known to play a role in combustion chemistry. Since interstellar PAHs are typically exposed to abundant atomic hydrogen and are thought to originate under pseudo-combustion conditions in carbon-rich circumstellar shells, such species may represent an important component of the interstellar PAH population. Furthermore, species larger than 50 carbon atoms are more representative of the size of the typical interstellar PAH. Overall, as has been the case for previous studies of PAH radical cations, the general pattern of band positions and intensities are consistent with that of the interstellar infrared emission spectrum. In addition, the spectra of closed-shell and open-shell cations are found to converge with increasing molecular size and are found to be relatively similar for species containing about 50 carbon atoms.

  17. Political experiments that matter: Ordering democracy from experimental sites.

    PubMed

    Laurent, Brice

    2016-10-01

    Some recent work in STS has discussed various forms of 'political experiments'. But why and how do experiments matter, and for whom? Answering these questions requires that one leave the locality of the experimental site and account for the construction of wider spaces wherein experiments matter. Using examples related to the public debate on, critique and government of nanotechnology in France, the article identifies three of these spaces. The first one is characterized by the replication of technologies of participation, the second by the conduct of radical critique, and the third by the constitution of objects of government. Overall, the description of these spaces helps describe the current (and incomplete) transformation of French democracy, as the public administration attempts to include new elements, such as 'citizens as locals' or 'substances in a nanoparticulate state', in the French polity. Thus, the study of political experiments proposed here offers analytical entry points for an examination of democratic ordering.

  18. Divalent Cation Removal by Donnan Dialysis for Improved Reverse Electrodialysis.

    PubMed

    Rijnaarts, Timon; Shenkute, Nathnael T; Wood, Jeffery A; de Vos, Wiebe M; Nijmeijer, Kitty

    2018-05-07

    Divalent cations in feedwater can cause significant decreases in efficiencies for membrane processes, such as reverse electrodialysis (RED). In RED, power is harvested from the mixing of river and seawater, and the obtainable voltage is reduced and the resistance is increased if divalent cations are present. The power density of the RED process can be improved by removing divalent cations from the fresh water. Here, we study divalent cation removal from fresh water using seawater as draw solution in a Donnan dialysis (DD) process. In this way, a membrane system with neither chemicals nor electrodes but only natural salinity gradients can be used to exchange divalent cations. For DD, the permselectivity of the cation exchange membrane is found to be crucial as it determines the ability to block salt leakage (also referred to as co-ion transport). Operating DD using a membrane stack achieved a 76% reduction in the divalent cation content in natural fresh water with residence times of just a few seconds. DD pretreated fresh water was then used in a RED process, which showed improved gross and net power densities of 9.0 and 6.3%, respectively. This improvement is caused by a lower fresh water resistance (at similar open circuit voltages), due to exchange of divalent for monovalent cations.

  19. The fragmentation of ethanol cation under an electric field: An ab initio/RRKM study

    NASA Astrophysics Data System (ADS)

    Lu, Hsiu-Feng; Li, F.-Y.; Lin, Chun-Chin; Nagaya, K.; Chao, Ito; Lin, S. H.

    2007-08-01

    We present a theoretical study of ethanol cation under an electric field due to the existence of laser field in order to understand the influence of electric field on the mass spectrum of ethanol. The electric field was applied to the four major reaction channels of an ethanol cation, such as the conversion between C 2H 5OH + and c-C 2H 5OH +, CH 3-elimination and two α-H-eliminations, respectively. The correlation between product distribution and field strength is quite complex due to the different responses of the reactants and transition states toward the external electric field. This makes the product distribution change as field strength varies.

  20. Effect of synthesis methods with different annealing temperatures on micro structure, cations distribution and magnetic properties of nano-nickel ferrite

    NASA Astrophysics Data System (ADS)

    El-Sayed, Karimat; Mohamed, Mohamed Bakr; Hamdy, Sh.; Ata-Allah, S. S.

    2017-02-01

    Nano-crystalline NiFe2O4 was synthesized by citrate and sol-gel methods at different annealing temperatures and the results were compared with a bulk sample prepared by ceramic method. The effect of methods of preparation and different annealing temperatures on the crystallize size, strain, bond lengths, bond angles, cations distribution and degree of inversions were investigated by X-ray powder diffraction, high resolution transmission electron microscope, Mössbauer effect spectrometer and vibrating sample magnetometer. The cations distributions were determined at both octahedral and tetrahedral sites using both Mössbauer effect spectroscopy and a modified Bertaut method using Rietveld method. The Mössbauer effect spectra showed a regular decrease in the hyperfine field with decreasing particle size. Saturation magnetization and coercivity are found to be affected by the particle size and the cations distribution.

  1. Episodic Salinization of Urban Rivers: Potential Impacts on Carbon, Cation, and Nutrient Fluxes

    NASA Astrophysics Data System (ADS)

    Haq, S.; Kaushal, S.

    2017-12-01

    Human dominated watersheds are subjected to an array of salt inputs (e.g. road salts), and in urban areas, infrastructure and impervious surfaces quickly drain applied road salts into the river channel. As a result, many streams experience episodic salinization over the course of hours to days following a snow event (e.g. road salt pulse), and long-term salinization over the course of seasons to decades. Salinization of streams can release contaminants (e.g. heavy metals), reduce biodiversity, and degrade drinking water quality. We investigated the water quality effects of episodic salinization in urban streams. Sediment and streamwater were incubated from twelve sites in the Baltimore-Washington Metropolitan Area under a range of sodium chloride treatments in a lab environment to mimic a vertical stream column with a sediment-water interface undergoing episodic salinization, and to characterize relationships between experimental salinization and nutrient/cation fluxes. Eight sites (Baltimore) exhibit a land use gradient and are routinely monitored within the Baltimore Ecosystem Study LTER project, and four sites (Washington DC) are suburban and offer a contrasting lithology and physiographic province. Our research suggests that salinization can mobilize total dissolved nitrogen, soluble reactive phosphorous, and base cations; potentially due to coupled biotic-abiotic processes, such as ion exchange, rapid nitrification, pH changes, and chloride-organic matter dispersal. The impact of salinization on dissolved inorganic and organic carbon varied between sites, potentially due to sediment composition, organic matter content, and ambient water quality. We contrasted the experimental results with measurements of salinization (specific conductance) and nutrients (nitrate) from real-time sensors operated by the US Geological Survey that encompass the same watersheds as our experimental sites. Sensor data was analyzed to provide insight on the timescales of salinity

  2. In situ remediation process using divalent metal cations

    DOEpatents

    Brady, Patrick V.; Khandaker, Nadim R.; Krumhansl, James L.; Teter, David M.

    2004-12-14

    An in situ process for treating ambient solid materials (e.g., soils, aquifer solids, sludges) by adding one or more divalent metal cations to the ambient solid material. The added divalent metal cations, such as Cu.sup.2+ or Zn.sup.2+, combine with metal oxide/hydroxides (e.g., ferric oxide/hydroxide or aluminum oxide/hydroxide) already present in the ambient solid material to form an effective sorbent material having a large number of positively-charged surface complexes that binds and immobilizes anionic contaminant species (e.g., arsenic or chromate). Divalent metal cations can be added, for example, by injecting an aqueous solution of CuSO.sub.4 into an aquifer contaminated with arsenic or chromate. Also, sludges can be stabilized against leaching of anionic contaminants through the addition of divalent metal cations. Also, an inexpensive sorbent material can be easily formed by mixing divalent metal cations with soil that has been removed from the ground.

  3. Location and valence state of strontium cations on the framework of a carbon dioxide selective porous silicoaluminophosphate

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

    Zhang, Li; Rivera-Ramos, Milton E.; Hernández-Maldonado, Arturo J.

    2014-05-28

    A Sr{sup 2+}-SAPO-34 material that displays superior CO2 adsorption selectivity and capacity was characterized via XPS and UV-vis spectroscopy to elucidate the valence state of strontium cations and framework silicon environment. Most importantly, the location of the strontium has been estimated from a Rietveld refinement analysis of synchrotron diffraction data. The XPS analysis indicated that the apparent valence state of the strontium is less than 2, an indication of its interaction with the large anionic framework. Furthermore, UV-vis tests pointed to changes in the silicon environment, plausibly related to this valence state or framework faulting. For the refinement, the analysismore » found that strontium occupied two unique sites: a site Sr1 slightly displaced from six-membered rings and a site Sr2 positioned at the top or bottom of the eight-membered rings. The latter position favors the interaction of the alkaline earth metal with CO{sub 2}, probably resulting in an enhanced electric field-quadrupole moment interaction.« less

  4. Cationic Biomimetic Particles of Polystyrene/Cationic Bilayer/Gramicidin for Optimal Bactericidal Activity.

    PubMed

    Xavier, Gabriel R S; Carmona-Ribeiro, Ana M

    2017-12-02

    Nanostructured particles of polystyrene sulfate (PSS) covered by a cationic lipid bilayer of dioctadecyldimethylammonium bromide (DODAB) incorporated gramicidin D (Gr) yielding optimal and broadened bactericidal activity against both Escherichia coli and Staphylococcus aureus . The adsorption of DODAB/Gr bilayer onto PSS nanoparticles (NPs) increased the zeta-average diameter by 8-10 nm, changed the zeta-potential of the NPs from negative to positive, and yielded a narrow size distributions for the PSS/DODAB/Gr NPs, which displayed broad and maximal microbicidal activity at very small concentrations of the antimicrobials, namely, 0.057 and 0.0057 mM DODAB and Gr, respectively. The results emphasized the advantages of highly-organized, nanostructured, and cationic particles to achieve hybrid combinations of antimicrobials with broad spectrum activity at considerably reduced DODAB and Gr concentrations.

  5. Behavior of cesium and thallium cations inside a calixarene cavity as probed by nuclear spin relaxation. Evidence of cation-pi interactions in water.

    PubMed

    Cuc, Diana; Bouguet-Bonnet, Sabine; Morel-Desrosiers, Nicole; Morel, Jean-Pierre; Mutzenhardt, Pierre; Canet, Daniel

    2009-08-06

    We have studied the complexes formed between the p-sulfonatocalix[4]arene and cesium or thallium metal cation, first by carbon-13 longitudinal relaxation of the calixarene molecule at two values of the magnetic field B(0). From the longitudinal relaxation times of an aromatic carbon directly bonded to a proton, thus subjected essentially to the dipolar interaction with that proton, we could obtain the correlation time describing the reorientation of the CH bond. The rest of this study has demonstrated that it is also the correlation time describing the tumbling of the whole calixarene assembly. From three non-proton-bearing carbons of the aromatic cycles (thus subjected to the chemical shift anisotropy and dipolar mechanisms), we have been able to determine the variation of the chemical shift anisotropy when going from the free to the complex form of the calixarene. These variations not only provide the location of the cation inside the calixarene cavity but also constitute a direct experimental proof of the cation-pi interactions. These results are complemented by cesium and thallium relaxation measurements performed again at two values of the magnetic field B(0). An estimation of the mean distance between the cation and the calixarene protons could be obtained. These measurements have also revealed an important chemical shift anisotropy of thallium upon complexation.

  6. Current scenario of peptide-based drugs: the key roles of cationic antitumor and antiviral peptides

    PubMed Central

    Mulder, Kelly C. L.; Lima, Loiane A.; Miranda, Vivian J.; Dias, Simoni C.; Franco, Octávio L.

    2013-01-01

    Cationic antimicrobial peptides (AMPs) and host defense peptides (HDPs) show vast potential as peptide-based drugs. Great effort has been made in order to exploit their mechanisms of action, aiming to identify their targets as well as to enhance their activity and bioavailability. In this review, we will focus on both naturally occurring and designed antiviral and antitumor cationic peptides, including those here called promiscuous, in which multiple targets are associated with a single peptide structure. Emphasis will be given to their biochemical features, selectivity against extra targets, and molecular mechanisms. Peptides which possess antitumor activity against different cancer cell lines will be discussed, as well as peptides which inhibit virus replication, focusing on their applications for human health, animal health and agriculture, and their potential as new therapeutic drugs. Moreover, the current scenario for production and the use of nanotechnology as delivery tool for both classes of cationic peptides, as well as the perspectives on improving them is considered. PMID:24198814

  7. Cation distributions on rapidly solidified cobalt ferrite

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

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

  8. Prussian Blue Coated Electrode as a Sensor for Electroinactive Cations in Aqueous Solutions

    ERIC Educational Resources Information Center

    Byrd, Houston; Chapman, Blake E.; Talley, Christopher L.

    2013-01-01

    Prussian Blue (PB) is an excellent material as a sensor for electroinactive cations because of its electrochemical behavior and its zeolytic character. A simple 3-h laboratory designed for a quantitative analysis or an instrumental methods course is reported. This laboratory studies the transport of various cations into a PB-modified electrode…

  9. Cation-enhanced capillary electrophoresis separation of atropoisomer anions.

    PubMed

    Na, Yun-Cheol; Berthod, Alain; Armstrong, Daniel W

    2015-12-01

    CE was used to study the separation of the atropoisomers of four phosphoric acids and two sulfonic acids and the enantiomers of two phosphoric acids. All solutes are in their anionic forms in aqueous electrolytes. The chiral additives were two hydroxypropyl cyclodextrins (CDs) and cyclofructan 6 (CF6). The CDs were able to separate four solutes and the CF6 additive could separate only one: 1,1'-binaphthyl-2,2'-diyl hydrogenphosphate (BHP). Since CF6 is able to bind with cations, nitrate of alkaline metals, Ba(2+) , and Pb(2+) were added, greatly improving the BHP separation at the expense of longer migration times. There seems to be a link between CF6-cation-binding constants and BHP resolution factors. Cation additions were also performed with CD selectors that are less prone to form complexes with cations. Significant improvements of enantiomer or atropoisomer separations were observed also associated with longer migration times. It is speculated that the anionic solutes associate with the added cations forming larger entities better differentiated by CDs. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Bending and breaking of stripes in a charge ordered manganite.

    PubMed

    Savitzky, Benjamin H; El Baggari, Ismail; Admasu, Alemayehu S; Kim, Jaewook; Cheong, Sang-Wook; Hovden, Robert; Kourkoutis, Lena F

    2017-12-01

    In charge-ordered phases, broken translational symmetry emerges from couplings between charge, spin, lattice, or orbital degrees of freedom, giving rise to remarkable phenomena such as colossal magnetoresistance and metal-insulator transitions. The role of the lattice in charge-ordered states remains particularly enigmatic, soliciting characterization of the microscopic lattice behavior. Here we directly map picometer scale periodic lattice displacements at individual atomic columns in the room temperature charge-ordered manganite Bi 0.35 Sr 0.18 Ca 0.47 MnO 3 using aberration-corrected scanning transmission electron microscopy. We measure transverse, displacive lattice modulations of the cations, distinct from existing manganite charge-order models. We reveal locally unidirectional striped domains as small as ~5 nm, despite apparent bidirectionality over larger length scales. Further, we observe a direct link between disorder in one lattice modulation, in the form of dislocations and shear deformations, and nascent order in the perpendicular modulation. By examining the defects and symmetries of periodic lattice displacements near the charge ordering phase transition, we directly visualize the local competition underpinning spatial heterogeneity in a complex oxide.

  11. Development of a novel method to determine the concentration of heavy metal cations: application of the specific interaction between heavy metal cation and mismatch DNA base pair.

    PubMed

    Kozasa, Tetsuo; Miyakawa, Yukako; Fukushi, Miyako; Ono, Akira; Torigoe, Hidetaka

    2009-01-01

    We have already found that Hg(II) cation specifically binds to T:T mismatch base pair in heteroduplex DNA, which increases the melting temperature of heteroduplex DNA involving T:T mismatch base pair by about 4 degrees C. We have also found that Ag(I) cation specifically binds to C:C mismatch base pair in heteroduplex DNA, which increases the melting temperature of heteroduplex DNA involving C:C mismatch base pair by about 4 degrees C. Using the specific interaction, we developed a novel sensor to determine the concentration of each of Hg(II) and Ag(I) cation. The sensor is composed of a dye-labelled T-rich or C-rich DNA oligonucleotide, F2T6W2D: 5'-Fam-T(2)CT(2)CT(2)C(4)T(2)GT(2)GT(2)-Dabcyl-3' or F2C6W2D: 5'-Fam-C(2)TC(2)TC(2)T(4)C(2)AC(2)AC(2)-Dabcyl-3', where 6-carboxyfluorescein (Fam) is a fluorophore and Dabcyl is a quencher. The addition of Hg(II) cation decreased the intensity of Fam emission of F2T6W2D at 520 nm in a concentration-dependent manner. Also, the addition of Ag(I) cation decreased the intensity of Fam emission of F2C6W2D at 520 nm in a concentration-dependent manner. We conclude that, using the novel sensor developed in this study, the concentration of each of Hg(II) and Ag(I) cation can be determined from the intensity of Fam emission at 520 nm.

  12. Triphenylphosphonium cation: a valuable functional group for antimicrobial photodynamic therapy.

    PubMed

    Bresolí-Obach, Roger; Gispert, Ignacio; García Peña, Diego; Boga, Sonia; Gulias, Óscar; Agut, Montserrat; Vázquez, M Eugenio; Nonell, Santi

    2018-06-08

    Light-mediated killing of pathogens by cationic photosensitisers is a promising antimicrobial approach that avoids the development of resistance inherent to the use of antimicrobials. In this study, we demonstrate that modification of different photosensitisers with the triphenylphosphonium cation yields derivatives with excellent photoantimicrobial activity against Gram-positive bacteria (i.e., S. aureus and E. faecalis). Thus, the triphenylphosphonium functional group should be considered for the development of photoantimicrobials for the selective killing of Gram-positive bacteria in the presence of Gram-negative species. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

  13. Surface modification of ZSM-5 zeolite: effect of cation on selective conversion of biomass-derived oil

    NASA Astrophysics Data System (ADS)

    Widayatno, W. B.

    2017-04-01

    This paper reports the surface modification of high silica ZSM-5 zeolite, particularly emphasizing the effect of cation type on selective conversion of biomass-derived oil. XRD spectra of the NaOH-treated HZSM-5 showed notable crystallinity decrease at specific crystal plane orientation. The N2-physisorption tests confirmed mesoporosity evolution as NaOH concentration was increased. NH3-desorption tests revealed a significant change on surface acidity which involved realumination and cation replacement processes. The utilization of untreated HZSM-5 as well as hierarchical NaZSM-5 for catalytic conversion of bio-oil showed the effect of cation type and mesoporosity on chemicals distribution. The untreated HZSM-5 showed high selectivity to aromatics, which degraded gradually due to deactivation and poisoning of the acid sites. Meanwhile, hierarchical NaZSM-5 showed high selectivity to phenolic compound, which became more stable for 0.4M NaOH-treated zeolite (Na04). The current findings provide an additional insight on the potentials of NaZSM-5 for bio-oil valorization.

  14. Properties of a cationic peroxidase from Citrus jambhiri cv. Adalia.

    PubMed

    Mohamed, Saleh A; El-Badry, Mohamed O; Drees, Ehab A; Fahmy, Afaf S

    2008-08-01

    The major pool of peroxidase activity is present in the peel of some Egyptian citrus species and cultivars compared to the juice and pulp. Citrus jambhiri cv. Adalia had the highest peroxidase activity among the examined species. Four anionic and one cationic peroxidase isoenzymes from C. jambhiri were detected using the purification procedure including ammonium sulfate precipitation, chromatography on diethylaminoethanol-cellulose, carboxymethyl-cellulose, and Sephacryl S-200 columns. Cationic peroxidase POII is proved to be pure, and its molecular weight was 56 kDa. A study of substrate specificity identified the physiological role of POII, which catalyzed the oxidation of some phenolic substrates in the order of o-phenylenediamine > guaiacol > o-dianisidine > pyrogallol > catechol. The kinetic parameters (K (m), V (max), and V (max)/K (m)) of POII for hydrolysis toward H2O2 and electron donor substrates were studied. The enzyme had pH and temperature optima at 5.5 and 40 degrees C, respectively. POII was stable at 10-40 degrees C and unstable above 50 degrees C. The thermal inactivation profile of POII is biphasic and characterized by a rapid decline in activity on exposure to heat. The most of POII activity (70-80%) was lost at 50, 60, and 70 degrees C after 15, 10, and 5 min of incubation, respectively. Most of the examined metal ions had a very slight effect on POII except of Li+, Zn2+, and Hg2+, which had partial inhibitory effects. In the present study, the instability of peroxidase above 50 degrees C makes the high temperature short time treatment very efficient for the inactivation of peel peroxidase contaminated in orange juice to avoid the formation of off-flavors.

  15. Structural evolution of the methane cation in subfemtosecond photodynamics

    NASA Astrophysics Data System (ADS)

    Mondal, T.; Varandas, A. J. C.

    2015-07-01

    An ab initio quantum dynamics study has been performed to explore the structural rearrangement of ground state CH 4+ in subfemtosecond resolved photodynamics. The method utilizes time-dependent wave-packet propagation on the X ˜ 2 T 2 electronic manifold of the title cation in full dimensionality, including nonadiabatic coupling of the three electronic sheets. Good agreement is obtained with recent experiments [Baker et al., Science 312, 424 (2006)] which use high-order harmonic generation to probe the attosecond proton dynamics. The novel results provide direct theoretical support of the observations while unravelling the underlying details. With the geometrical changes obtained by calculating the expectation values of the nuclear coordinates as a function of time, the structural evolution is predicted to begin through activation of the totally symmetric a1 and doubly degenerate e modes. While the former retains the original Td symmetry of the cation, the Jahn-Teller active e mode conducts it to a D2d structure. At ˜1.85 fs, the intermediate D2d structure is further predicted to rearrange to local C2v minimum geometry via Jahn-Teller active bending vibrations of t2 symmetry.

  16. Theoretical Investigation of Anharmonic Effects Observed in the Infrared Spectra of the Formaldehyde Cation and its Hydroxymethylene Isomer

    NASA Astrophysics Data System (ADS)

    Madison, Lindsey R.; Mosley, Jonathan; Mauney, Daniel; Duncan, Michael A.; McCoy, Anne B.

    2016-06-01

    Formaldehyde is the smallest organic molecule and is a prime candidate for a thorough investigation regarding the anharmonic approximations made in computationally modeling its infrared spectrum. Mass-selected ion spectroscopy was used to detect mass 30 cations which include of HCOH^+ and CH_2O^+. In order to elucidate the differences between the structures of these isomers, infrared spectroscopy was performed on the mass 30 cations using Ar predissociation. Interestingly, several additional spectral features are observed that cannot be explained by the fundamental OH and CH stretch vibrations alone. By including anharmonic coupling between OH and CH stretching and various overtones and combination bands involving lower frequency vibrations, we are able to identify how specific modes couple and lead to the experimentally observed spectral features. We combine straight-forward, ab initio calculations of the anharmonic frequencies of the mass 30 cations with higher order, adiabatic approximations and Fermi resonance models. By including anharmonic effects we are able to confirm that the isomers of the CH_2O^+\\cdotAr system have substantially different, and thus distinguishable, IR spectra and that many of the features can only be explained with anharmonic treatments.

  17. Reactive p-block cations stabilized by weakly coordinating anions

    PubMed Central

    Engesser, Tobias A.; Lichtenthaler, Martin R.; Schleep, Mario

    2016-01-01

    The chemistry of the p-block elements is a huge playground for fundamental and applied work. With their bonding from electron deficient to hypercoordinate and formally hypervalent, the p-block elements represent an area to find terra incognita. Often, the formation of cations that contain p-block elements as central ingredient is desired, for example to make a compound more Lewis acidic for an application or simply to prove an idea. This review has collected the reactive p-block cations (rPBC) with a comprehensive focus on those that have been published since the year 2000, but including the milestones and key citations of earlier work. We include an overview on the weakly coordinating anions (WCAs) used to stabilize the rPBC and give an overview to WCA selection, ionization strategies for rPBC-formation and finally list the rPBC ordered in their respective group from 13 to 18. However, typical, often more organic ion classes that constitute for example ionic liquids (imidazolium, ammonium, etc.) were omitted, as were those that do not fulfill the – naturally subjective – “reactive”-criterion of the rPBC. As a rule, we only included rPBC with crystal structure and only rarely refer to important cations published without crystal structure. This collection is intended for those who are simply interested what has been done or what is possible, as well as those who seek advice on preparative issues, up to people having a certain application in mind, where the knowledge on the existence of a rPBC that might play a role as an intermediate or active center may be useful. PMID:26612538

  18. Unexpected Actinyl Cation-Directed Structural Variation in Neptunyl(VI) A-Type Tri-lacunary Heteropolyoxotungstate Complexes

    DOE PAGES

    Berg, John M.; Gaunt, Andrew J.; May, Iain; ...

    2015-04-22

    A-type tri-lacunary heteropolyoxotungstate anions (e.g., [PW 9O 34] 9-, [AsW 9O 34] 9-, [SiW 9O 34] 10- and [GeW 9O 34] 10-) are multi-dentate oxygen donor ligands that readily form sandwich complexes with actinyl cations ({UO 2} 2+, {NpO 2} +, {NpO 2} 2+ & {PuO 2} 2+) in near neutral/slightly alkaline aqueous solutions. Two or three actinyl cations are sandwiched between two trilacunary anions, with additional cations (Na +, K + or NH 4 +) also often held within the cluster. Studies thus far have indicated that it is these additional +I cations, rather than the specific actinylmore » cation, that direct the structural variation in the complexes formed. We now report the structural characterization of the neptunyl (VI) cluster complex (NH 4) 13 [Na(NpO 2) 2(A-α- PW 9O 34) 2]·12H 2O. The anion in this complex, [Na(NpO 2) 2(PW 9O 34) 2] 13-, contains one Na + cation and two {NpO 2} 2+ cations held between two [PW 9O 34] 9- anions – with an additional partial occupancy NH 4 + or {NpO 2} 2+ cation also present. In the analogous uranium (VI) system, under similar reaction conditions that includes an excess of NH 4Cl in the parent solution, it was previously shown that [(NH 4) 2(U VIO 2) 2(A-PW 9O 34) 2] 12- is the dominant species in both solution and the crystallized salt. Spectroscopic studies provide further proof of differences in the observed chemistry for the {NpO 2} 2+/[PW 9O 34] 9- and {UO 2} 2+/[PW 9O 34] 9- systems, both in solution and in solid state complexes crystallized from comparable salt solutions. The work revealed that varying the actinide element (Np vs. U) can indeed measurably impact structure and complex stability in the cluster chemistry of actinyl (VI) cations with A-type tri-lacunary heteropolyoxotungstate anions.« less

  19. Monovalent Cation Doping of CH3NH3PbI3 for Efficient Perovskite Solar Cells.

    PubMed

    Abdi-Jalebi, Mojtaba; Dar, M Ibrahim; Sadhanala, Aditya; Senanayak, Satyaprasad P; Grätzel, Michael; Friend, Richard H

    2017-03-19

    Here, we demonstrate the incorporation of monovalent cation additives into CH3NH3PbI3 perovskite in order to adjust the optical, excitonic, and electrical properties. The possibility of doping was investigated by adding monovalent cation halides with similar ionic radii to Pb 2+ , including Cu + , Na + , and Ag + . A shift in the Fermi level and a remarkable decrease of sub-bandgap optical absorption, along with a lower energetic disorder in the perovskite, was achieved. An order-of-magnitude enhancement in the bulk hole mobility and a significant reduction of transport activation energy within an additive-based perovskite device was attained. The confluence of the aforementioned improved properties in the presence of these cations led to an enhancement in the photovoltaic parameters of the perovskite solar cell. An increase of 70 mV in open circuit voltage for AgI and a 2 mA/cm 2 improvement in photocurrent density for NaI- and CuBr-based solar cells were achieved compared to the pristine device. Our work paves the way for further improvements in the optoelectronic quality of CH3NH3PbI3 perovskite and subsequent devices. It highlights a new avenue for investigations on the role of dopant impurities in crystallization and controls the electronic defect density in perovskite structures.

  20. Monovalent Cation Doping of CH3NH3PbI3 for Efficient Perovskite Solar Cells

    PubMed Central

    Abdi-Jalebi, Mojtaba; Dar, M. Ibrahim; Sadhanala, Aditya; Senanayak, Satyaprasad P.; Grätzel, Michael; Friend, Richard H.

    2017-01-01

    Here, we demonstrate the incorporation of monovalent cation additives into CH3NH3PbI3 perovskite in order to adjust the optical, excitonic, and electrical properties. The possibility of doping was investigated by adding monovalent cation halides with similar ionic radii to Pb2+, including Cu+, Na+, and Ag+. A shift in the Fermi level and a remarkable decrease of sub-bandgap optical absorption, along with a lower energetic disorder in the perovskite, was achieved. An order-of-magnitude enhancement in the bulk hole mobility and a significant reduction of transport activation energy within an additive-based perovskite device was attained. The confluence of the aforementioned improved properties in the presence of these cations led to an enhancement in the photovoltaic parameters of the perovskite solar cell. An increase of 70 mV in open circuit voltage for AgI and a 2 mA/cm2 improvement in photocurrent density for NaI- and CuBr-based solar cells were achieved compared to the pristine device. Our work paves the way for further improvements in the optoelectronic quality of CH3NH3PbI3 perovskite and subsequent devices. It highlights a new avenue for investigations on the role of dopant impurities in crystallization and controls the electronic defect density in perovskite structures. PMID:28362369

  1. Does the cation really matter? The effect of modifying an ionic liquid cation on an SN2 process.

    PubMed

    Tanner, Eden E L; Yau, Hon Man; Hawker, Rebecca R; Croft, Anna K; Harper, Jason B

    2013-09-28

    The rate of reaction of a Menschutkin process in a range of ionic liquids with different cations was investigated, with temperature-dependent kinetic data giving access to activation parameters for the process in each solvent. These data, along with molecular dynamics simulations, demonstrate the importance of accessibility of the charged centre on the cation and that the key interactions are of a generalised electrostatic nature.

  2. Quantum Effects in Cation Interactions with First and Second Coordination Shell Ligands in Metalloproteins

    PubMed Central

    2015-01-01

    Despite decades of investigations, the principal mechanisms responsible for the high affinity and specificity of proteins for key physiological cations K+, Na+, and Ca2+ remain a hotly debated topic. At the core of the debate is an apparent need (or lack thereof) for an accurate description of the electrostatic response of the charge distribution in a protein to the binding of an ion. These effects range from partial electronic polarization of the directly ligating atoms to long-range effects related to partial charge transfer and electronic delocalization effects. While accurate modeling of cation recognition by metalloproteins warrants the use of quantum-mechanics (QM) calculations, the most popular approximations used in major biomolecular simulation packages rely on the implicit modeling of electronic polarization effects. That is, high-level QM computations for ion binding to proteins are desirable, but they are often unfeasible, because of the large size of the reactive-site models and the need to sample conformational space exhaustively at finite temperature. Several solutions to this challenge have been proposed in the field, ranging from the recently developed Drude polarizable force-field for simulations of metalloproteins to approximate tight-binding density functional theory (DFTB). To delineate the usefulness of different approximations, we examined the accuracy of three recent and commonly used theoretical models and numerical algorithms, namely, CHARMM C36, the latest developed Drude polarizable force fields, and DFTB3 with the latest 3OB parameters. We performed MD simulations for 30 cation-selective proteins with high-resolution X-ray structures to create ensembles of structures for analysis with different levels of theory, e.g., additive and polarizable force fields, DFTB3, and DFT. The results from DFT computations were used to benchmark CHARMM C36, Drude, and DFTB3 performance. The explicit modeling of quantum effects unveils the key

  3. UV absorption spectrum of allene radical cations in solid argon

    NASA Astrophysics Data System (ADS)

    Chin, Chih-Hao; Lin, Meng-Yeh; Huang, Tzu-Ping; Wu, Yu-Jong

    2018-05-01

    Electron bombardment during deposition of an Ar matrix containing a small proportion of allene generated allene cations. Further irradiation of the matrix sample at 385 nm destroyed the allene cations and formed propyne cations in solid Ar. Both cations were identified according to previously reported IR absorption bands. Using a similar technique, we recorded the ultraviolet absorption spectrum of allene cations in solid Ar. The vibrationally resolved progression recorded in the range of 266-237 nm with intervals of about 800 cm-1 was assigned to the A2E ← X2E transition of allene cations, and the broad continuum absorption recorded in the region of 229-214 nm was assigned to their B2A1 ← X2E transition. These assignments were made based on the observed photolytic behavior of the progressions and the vertical excitation energies and oscillator strengths calculated using time-dependent density functional theory.

  4. The multiple nucleotide-divalent cation binding modes of Saccharomyces cerevisiae CK2α indicate a possible co-substrate hydrolysis product (ADP/GDP) release pathway.

    PubMed

    Liu, Huihui; Wang, Hong; Teng, Maikun; Li, Xu

    2014-02-01

    CK2 is a ubiquitous and conserved protein kinase in eukaryotic organisms and is important in many biological processes. It is unique in maintaining constitutive activity and in using both ATP and GTP as phosphor donors. In this study, crystal structures of recombinant Saccharomyces cerevisiae CK2α (scCK2α) complexed with GMPPNP, ATP and AMPPN with either Mg2+ or Mn2+ as the coordinated divalent cation are presented. The overall structure of scCK2α shows high similarity to its homologous proteins by consisting of two domains with the co-substrate lying in the cleft between them. However, three characteristic features distinguish scCK2α from its homologues. Firstly, the Lys45-Glu53 and Arg48-Glu53 interactions in scCK2α lead Lys50 to adopt a unique conformation that is able to stabilize the γ-phosphate of the co-substrate, which makes the existence of the `essential divalent cation' not so essential. The multiple nucleotide-divalent cation binding modes of the active site of scCK2α are apparently different from the two-divalent-cation-occupied active site of Zea mays CK2α and human CK2α. Secondly, conformational change of Glu53 in scCK2α-AMPPN breaks its interaction with Lys45 and Arg48; as a result, the co-substrate binding pocket becomes more open. This may suggest a clue to a possible ADP/GDP-release pathway, because the NE1 atom of the Trp in the `DWG motif' of CK2α forms a hydrogen bond to the O atom of Leu212, which seems to make ADP release by means of the `DFG-in flip to DFG-out' model found in most eukaryotic protein kinases impossible. Coincidentally, two sulfate ions which may mimic two phosphate groups were captured by Arg161 and Lys197 around the pocket. Mutagenesis and biochemical experiments on R161A and K197A mutants support the above proposal. Finally, scCK2α is unique in containing an insertion region whose function had not been identified in previous research. It is found that the insertion region contributes to maintaining the

  5. An ammonia-stabilized mixed-cation borohydride: synthesis, structure and thermal decomposition behavior.

    PubMed

    Yang, Yanjing; Liu, Yongfeng; Wu, Hui; Zhou, Wei; Gao, Mingxia; Pan, Hongge

    2014-01-07

    We demonstrate the synthesis, crystal structure and thermal decomposition behavior of a novel ammonia-stabilized mixed-cation borohydride where the NH3 groups enable the coexistence of Li and Mg cations as an "assistant". Li2Mg(BH4)4·6NH3, which is comprised of orderly arranged Mg[NH3]6(2+) ammine complexes and Li2[BH4]4(2-) complex anions, was synthesized by the mechanochemical reaction between Mg(BH4)2·6NH3 and LiBH4. This novel compound crystallizes in a tetragonal P4(3)2(1)2 (No. 96) structure with lattice parameters a = b = 10.7656(8) Å and c = 13.843(1) Å with very short dihydrogen bonds, which determine a very low onset temperature of 80 °C for hydrogen release and are also responsible for the nucleation of Li2Mg(BH4)4·3NH3 as a decomposition intermediate. Mechanistic investigations on the thermal decomposition showed that the H(δ+)-H(δ-) combination in the ammonia-stabilized mixed-cation borohydride was significantly enhanced due to the strengthened Mg-N bonds. Upon heating, 11.02 moles of H2 (equivalent to 11.1 wt%) and 3.07 moles of NH3 are evolved from one mole of Li2Mg(BH4)4·6NH3 with a three-step reaction. The insights into the formation mechanism of ammonia-stabilized mixed-cation borohydride and the role played by NH3 group are very useful as a guideline for the design and synthesis of novel B-N-based materials with high hydrogen content.

  6. Degradable cationic nanohydrogel particles for stimuli-responsive release of siRNA.

    PubMed

    Nuhn, Lutz; Braun, Lydia; Overhoff, Iris; Kelsch, Annette; Schaeffel, David; Koynov, Kaloian; Zentel, Rudolf

    2014-12-01

    Well-defined nanogels have become quite attractive as safe and stable carriers for siRNA delivery. However, to avoid nanoparticle accumulation, they need to provide a stimuli-responsive degradation mechanism that can be activated at the payload's site of action. In this work, the synthetic concept for generating well-defined nanohydrogel particles is extended to incorporate disulfide cross-linkers into a cationic nanonetwork for redox-triggered release of oligonucleotide payload as well as nanoparticle degradation under reductive conditions of the cytoplasm. Therefore, a novel disulfide-modified spermine cross-linker is designed that both allows disassembly of the nanogel as well as removal of cationic charge from residual polymer fragments. The degradation process is monitored by scanning electron microscopy (SEM) and fluorescence correlation spectroscopy (FCS). Moreover, siRNA release is analyzed by agarose gel electrophoresis and a fluorescent RNA detection assay. The results exemplify the versatility of the applied nanogel manufacturing process, which allows alternative stimuli-responsive core cross-linkers to be integrated for triggered oligonucleotide release as well as effective biodegradation for reduced nanotoxicity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    PubMed Central

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

    2015-01-01

    Soil particle interactions are strongly influenced by the concentration, valence and ion species and the pH of the bulk solution, which will also affect aggregate stability and particle transport. In this study, we investigated clay aggregate stability in the presence of different alkali ions (Li+, Na+, K+, and Cs+) at concentrations from10−5 to 10−1 mol L−1. Strong specific ion effects on clay aggregate stability were observed, and showed the order Cs+>K+>Na+>Li+. We found that it was not the effects of ion size, hydration, and dispersion forces in the cation–surface interactions but strong non-classic polarization of adsorbed cations that resulted in these specific effects. In this study, the non-classic dipole moments of each cation species resulting from the non-classic polarization were estimated. By comparing non-classic dipole moments with classic values, the observed dipole moments of adsorbed cations were up to 104 times larger than the classic values for the same cation. The observed non-classic dipole moments sharply increased with decreasing electrolyte concentration. We conclude that strong non-classic polarization could significantly suppress the thickness of the diffuse layer, thereby weakening the electric field near the clay surface and resulting in improved clay aggregate stability. Even though we only demonstrated specific ion effects on aggregate stability with several alkali ions, our results indicate that these effects could be universally important in soil aggregate stability. PMID:25874864

  8. Antimicrobial particles from cationic lipid and polyelectrolytes.

    PubMed

    Melo, Letícia D; Mamizuka, Elsa M; Carmona-Ribeiro, Ana M

    2010-07-20

    Hybrid nanoparticles from cationic lipid and polymers were prepared and characterized regarding physical properties and antimicrobial activity. Carboxymethylcellulose (CMC) and polydiallyldimethylammonium chloride (PDDA) were sequentially added to cationic bilayer fragments (BF) prepared from ultrasonic dispersion in water of the synthetic and cationic lipid dioctadecyldimethylammonium bromide (DODAB). Particles thus obtained were characterized by dynamic light-scattering for determination of z-average diameter (Dz) and zeta-potential (zeta). Antimicrobial activity of the DODAB BF/CMC/PDDA particles against Pseudomonas aeruginosa or Staphylococcus aureus was determined by plating and CFU counting over a range of particle compositions. DODAB BF/CMC/PDDA particles exhibited sizes and zeta-potentials strictly dependent on DODAB, CMC, and PDDA concentrations. At 0.1 mM DODAB, 0.1 mg/mL CMC, and 0.1 mg/mL PDDA, small cationic particles with Dz = 100 nm and zeta = 30 mV were obtained. At 0.5 mM DODAB, 0.5 mg/mL CMC and 0.5 mg/mL PDDA, large cationic particles with Dz = 470 nm and zeta = 50 mV were obtained. Both particulates were highly reproducible regarding physical properties and yielded 0% of P. aeruginosa viability (10(7) CFU/mL) at 1 or 2 microg/mL PDDA dissolved in solution or in form of particles, respectively. 99% of S. aureus cells died at 10 microg/mL PDDA alone or in small or large DODAB BF/CMC/PDDA particles. The antimicrobial effect was dependent on the amount of positive charge on particles and independent of particle size. A high microbicide potency for PDDA over a range of nanomolar concentrations was disclosed. P. aeruginosa was more sensitive to all cationic assemblies than S. aureus.

  9. Biotic ligand modeling approach: Synthesis of the effect of major cations on the toxicity of metals to soil and aquatic organisms.

    PubMed

    Ardestani, Masoud M; van Straalen, Nico M; van Gestel, Cornelis A M

    2015-10-01

    The biotic ligand model (BLM) approach is used to assess metal toxicity, taking into account the competition of other cations with the free metal ions for binding to the biotic ligand sites of aquatic and soil organisms. The bioavailable fraction of metals, represented by the free metal ion, is a better measure than the total concentration for assessing their potential risk to the environment. Because BLMs are relating toxicity to the fraction of biotic ligands occupied by the metal, they can be useful for investigating factors affecting metal bioaccumulation and toxicity. In the present review, the effects of major cations on the toxicity of metals to soil and aquatic organisms were comprehensively studied by performing a meta-analysis of BLM literature data. Interactions at the binding sites were shown to be species- and metal-specific. The main factors affecting the relationships between toxicity and conditional binding constants for metal binding at the biotic ligand appeared to be Ca(2+) , Mg(2+) , and protons. Other important characteristics of the exposure medium, such as levels of dissolved organic carbon and concentrations of other cations, should also be considered to obtain a proper assessment of metal toxicity to soil and aquatic organisms. © 2015 SETAC.

  10. Regeneration of Cation-Transport Capacity in HeLa Cell Membranes After Specific Blockade by Ouabain

    PubMed Central

    Vaughan, Gerald L.; Cook, John S.

    1972-01-01

    The cardiac glycoside, ouabain, inhibits alkali-cation transport in HeLa cells. It binds to 0.75 × 106 sites per cell, and the half-time for its dissociation is 16 hr. After partial blockade by ouabain, the cell generates new ouabain-binding sites, with total restoration of transport in 10% of a cell cycle(∼3 hr). This recovery requires protein synthesis and appears to be a response to altered cell-electrolyte content, since growth of cells in media with low K+ concentration enhances the titer of the transport enzyme in a fashion similar to the effect of ouabain. Totally blocked cells do not recover. PMID:4506784

  11. How the spontaneous insertion of amphiphilic imidazolium-based cations changes biological membranes: a molecular simulation study.

    PubMed

    Lim, Geraldine S; Jaenicke, Stephan; Klähn, Marco

    2015-11-21

    The insertion of 1-octyl-3-methylimidazolium cations (OMIM(+)) from a diluted aqueous ionic liquid (IL) solution into a model of a bacterial cell membrane is investigated. Subsequently, the mutual interactions of cations inside the membrane and their combined effect on membrane properties are derived. The ionic liquid solution and the membrane model are simulated using molecular dynamics in combination with empirical force fields. A high propensity of OMIM(+) for membrane insertion is observed, with a cation concentration at equilibrium inside the membrane 47 times larger than in the solvent. Once inserted, cations exhibit a weak effective attraction inside the membrane at a distance of 1.3 nm. At this free energy minimum, negatively charged phosphates of the phospholipids are sandwiched between two OMIM(+) to form energetically favorable OMIM(+)-phosphate-OMIM(+) types of coordination. The cation-cation association free energy is 5.9 kJ mol(-1), whereas the activation barrier for dissociation is 10.1 kJ mol(-1). Subsequently, OMIM(+) are inserted into the leaflet of the membrane bilayer that represents the extracellular side. The cations are evenly distributed with mutual cation distances according to the found optimum distance of 1.3 nm. Because of the short length of the cation alkyl chains compared to lipid fatty acids, voids are generated in the hydrophobic core of the membrane. These voids disorder the fatty acids, because they enable fatty acids to curl into these empty spaces and also cause a thinning of the membrane by 0.6 nm. Additionally, the membrane density increases at its center. The presence of OMIM(+) in the membrane facilitates the permeation of small molecules such as ammonia through the membrane, which is chosen as a model case for small polar solutes. The permeability coefficient of the membrane with respect to ammonia increases substantially by a factor of seven. This increase is caused by a reduction of the involved free energy barriers

  12. Effect of cation size and charge on the interaction between silica surfaces in 1:1, 2:1, and 3:1 aqueous electrolytes.

    PubMed

    Dishon, Matan; Zohar, Ohad; Sivan, Uri

    2011-11-01

    Application of two complementary AFM measurements, force vs separation and adhesion force, reveals the combined effects of cation size and charge (valency) on the interaction between silica surfaces in three 1:1, three 2:1, and three 3:1 metal chloride aqueous solutions of different concentrations. The interaction between the silica surfaces in 1:1 and 2:1 salt solutions is fully accounted for by ion-independent van der Waals (vdW) attraction and electric double-layer repulsion modified by cation specific adsorption to the silica surfaces. The deduced ranking of mono- and divalent cation adsorption capacity (adsorbability) to silica, Mg(2+) < Ca(2+) < Na(+) < Sr(2+) < K(+) < Cs(+), follows cation bare size as well as cation solvation energy but does not correlate with hydrated ionic radius or with volume or surface ionic charge density. In the presence of 3:1 salts, the coarse phenomenology of the force between the silica surfaces as a function of salt concentration resembles that in 1:1 and 2:1 electrolytes. Nevertheless, two fundamental differences should be noticed. First, the attraction between the silica surfaces is too large to be attributed solely to vdW force, hence implying an additional attraction mechanism or gross modification of the conventional vdW attraction. Second, neutralization of the silica surfaces occurs at trivalent cation concentrations that are 3 orders of magnitude smaller than those characterizing surface neutralization by mono- and divalent cations. Consequently, when trivalent cations are added to our cation adsorbability series the correlation with bare ion size breaks down abruptly. The strong adsorbability of trivalent cations to silica contrasts straightforward expectations based on ranking of the cationic solvation energies, thus suggesting a different adsorption mechanism which is inoperative or weak for mono- and divalent cations.

  13. Cation Exchange Water Softeners

    EPA Pesticide Factsheets

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

  14. Removal of anionic and cationic dyes with bioadsorbent oxidized chitosans.

    PubMed

    León, Orietta; Muñoz-Bonilla, Alexandra; Soto, Diana; Pérez, Daniela; Rangel, Medarda; Colina, Marinela; Fernández-García, Marta

    2018-08-15

    Different oxidized chitosans were prepared following various approaches, by thermo-acid oxidation or by using KMnO 4 /NaHSO 3 , (NH 4 ) 2 S 2 O 8 /NaHSO 3 and K 2 Cr 2 O 7 /NaHSO 3 redox pairs added sequentially or simultaneously. All these reactions pursue the formation of carboxylic groups which enhance their capability to remove model cationic and anionic dyes such as methylene blue and methyl orange, respectively. The resulting oxidized chitosans were structurally and thermally characterized by elemental analysis, infrared spectroscopy, nuclear magnetic resonance, scanning electron microscopy and thermogravimetry. The swelling capacity of these hydrogels was also determined as well as the remediation ability of dyes in different conditions. The results showed that the adsorption of methylene blue followed a pseudo second-order kinetics model, while the adsorption behavior was in agreement with the Langmuir isotherm model. Remarkably, the oxidized chitosans showed removal ability for both dyes cationic and anionic, which of great importance for application of these materials as versatile bioadsorbents. Copyright © 2018 Elsevier Ltd. All rights reserved.

  15. Multifunctional cationic polyurethanes designed for non-viral cancer gene therapy.

    PubMed

    Cheng, Jian; Tang, Xin; Zhao, Jie; Shi, Ting; Zhao, Peng; Lin, Chao

    2016-01-01

    Nano-polyplexes from bioreducible cationic polymers have a massive promise for cancer gene therapy. However, the feasibility of cationic polyurethanes for non-viral gene therapy is so far not well studied. In this work, a linear cationic polyurethane containing disulfide bonds, urethane linkages and protonable tertiary amino groups was successfully generated by stepwise polycondensation reaction between 2,2'-dithiodiethanol bis(p-nitrophenyl carbonate) and 1,4-bis(3-aminopropyl)piperazine (BAP). We confirmed that the cationic polyurethane (denoted as PUBAP) displayed superior gene delivery properties to its cationic polyamide analogue, thus causing higher in vitro transfection efficiency in MCF-7 and SKOV-3 cells. Besides, further folate-PEGylation and hydrophobic deoxycholic acid (DCA) conjugation to amino-containing PUBAP can be conducted to afford multifunctional polyurethane gene delivery system. After optimization, folate-decorated nano-polyplexes from the PUBAP conjugated with 8 folate-PEG chains and 12 DCA residues exhibited superb colloidal stability under physiological conditions, and performed rapid uptake via folate receptor-mediated endocytosis, efficient intracellular gene release and nucleus translocation into SKOV-3 cells in vitro and in vivo. Importantly, PUBAP based polyplexes possess low cytotoxicity as a result of PUBAP biodegradability. Therefore, marked growth inhibition of SKOV-3 tumor xenografted in Balb/c nude mice was achieved with negligible side effects on the mouse health after intravenous administration of PUBAP based polyplexes with a therapeutic plasmid encoding for TNF-related apoptosis-inducing ligand. This work provides a new insight into biomedical application of bio-responsive polyurethanes for cancer therapy. In this study, we have confirmed that disulfide-based cationic polyurethane presents a new non-viral vector for gene transfer and cancer gene therapy. The significance of this work includes: (1) design and synthesis of a

  16. High-temperature site preference and atomic short-range ordering characteristics of ternary alloying elements in γ'-Ni3Al intermetallics

    NASA Astrophysics Data System (ADS)

    Eriş, Rasim; Mekhrabov, Amdulla O.; Akdeniz, M. Vedat

    2017-10-01

    Remarkable high-temperature mechanical properties of nickel-based superalloys are correlated with the arrangement of ternary alloying elements in L12-type-ordered γ‧-Ni3Al intermetallics. In the current study, therefore, high-temperature site occupancy preference and energetic-structural characteristics of atomic short-range ordering (SRO) of ternary alloying X elements (X = Mo, W, Ta, Hf, Re, Ru, Pt or Co) in Ni75Al21.875X3.125 alloy systems have been studied by combining the statistico-thermodynamical theory of ordering and electronic theory of alloys in the pseudopotential approximation. Temperature dependence of site occupancy tendencies of alloying X element atoms has been predicted by calculating partial ordering energies and SRO parameters of Ni-Al, Ni-X and Al-X atomic pairs. It is shown that, all ternary alloying element atoms (except Pt) tend to occupy Al, whereas Pt atoms prefer to substitute for Ni sub-lattice sites of Ni3Al intermetallics. However, in contrast to other X elements, sub-lattice site occupancy characteristics of Re atoms appear to be both temperature- and composition-dependent. Theoretical calculations reveal that site occupancy preference of Re atoms switches from Al to both Ni and Al sites at critical temperatures, Tc, for Re > 2.35 at%. Distribution of Re atoms at both Ni and Al sub-lattice sites above Tc may lead to localised supersaturation of the parent Ni3Al phase and makes possible the formation of topologically close-packed (TCP) phases. The results of the current theoretical and simulation study are consistent with other theoretical and experimental investigations published in the literature.

  17. Size Dependent Cation Channel in Nanoporous Prussian Blue Lattice

    NASA Astrophysics Data System (ADS)

    Moritomo, Yutaka; Igarashi, Kazuhiro; Kim, Jungeun; Tanaka, Hiroshi

    2009-08-01

    Cation and/or molecule transfer within nanoporous materials can be utilized in, for example, electrochromic devices, hydrogen storage, molecular sensors, and molecular filters. Here, we investigated the mobilities of cations, Na+, K+, and Rb+, in vacancy-controlled Prussian blue film, NaxCo[Fe(CN)6]1-vzH2O (v is vacancy concentration) with a jungle gym structure. We found that only the smallest Na+ ions pass through the cubic planes of the lattice, while the larger cations, i.e., K+ and Rb+, take a detour channel along the [Fe(CN)6] vacancy. The size-dependent cation channel is well understood in terms of the potential curve derived by an ab initio total energy calculation.

  18. DFT study of the active site of the XoxF-type natural, cerium-dependent methanol dehydrogenase enzyme.

    PubMed

    Bogart, Justin A; Lewis, Andrew J; Schelter, Eric J

    2015-01-19

    Rare-earth metal cations have recently been demonstrated to be essential co-factors for the growth of the methanotrophic bacterium Methylacidiphilum fumariolicum SolV. A crystal structure of the rare-earth-dependent methanol dehydrogenase (MDH) includes a cerium cation in the active site. Herein, the Ce-MDH active site has been analyzed through DFT calculations. The results show the stability of the Ce(III)-pyrroloquinoline quinone (PQQ) semiquinone configuration. Calculations on the active oxidized form of this complex indicate a 0.81 eV stabilization of the PQQ(0) LUMO at cerium versus calcium, supporting the observation that the cerium cation in the active site confers a competitive advantage to Methylacidiphilum fumariolicum SolV. Using reported aqueous electrochemical data, a semi-empirical correlation was established based on cerium(IV/III) redox potentials. The correlation allowed estimation of the cerium oxidation potential of +1.35 V versus saturated calomel electrode (SCE) in the active site. The results are expected to guide the design of functional model complexes and alcohol-oxidation catalysts based on lanthanide complexes of biologically relevant quinones. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials

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

    Lee, Jinhyuk; Papp, Joseph K.; Clément, Raphaële J.

    Recent progress in the understanding of percolation theory points to cation-disordered lithium-excess transition metal oxides as high-capacity lithium-ion cathode materials. Nevertheless, the oxygen redox processes required for these materials to deliver high capacity can trigger oxygen loss, which leads to the formation of resistive surface layers on the cathode particles. Here, we demonstrate here that, somewhat surprisingly, fluorine can be incorporated into the bulk of disordered lithium nickel titanium molybdenum oxides using a standard solid-state method to increase the nickel content, and that this compositional modification is very effective in reducing oxygen loss, improving energy density, average voltage, and ratemore » performance. We argue that the valence reduction on the anion site, offered by fluorine incorporation, opens up significant opportunities for the design of high-capacity cation-disordered cathode materials.« less

  20. Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials

    DOE PAGES

    Lee, Jinhyuk; Papp, Joseph K.; Clément, Raphaële J.; ...

    2017-10-17

    Recent progress in the understanding of percolation theory points to cation-disordered lithium-excess transition metal oxides as high-capacity lithium-ion cathode materials. Nevertheless, the oxygen redox processes required for these materials to deliver high capacity can trigger oxygen loss, which leads to the formation of resistive surface layers on the cathode particles. Here, we demonstrate here that, somewhat surprisingly, fluorine can be incorporated into the bulk of disordered lithium nickel titanium molybdenum oxides using a standard solid-state method to increase the nickel content, and that this compositional modification is very effective in reducing oxygen loss, improving energy density, average voltage, and ratemore » performance. We argue that the valence reduction on the anion site, offered by fluorine incorporation, opens up significant opportunities for the design of high-capacity cation-disordered cathode materials.« less

  1. Infrared spectroscopy of matrix-isolated polycyclic aromatic hydrocarbon cations. 2. The members of the thermodynamically most favorable series through coronene

    NASA Technical Reports Server (NTRS)

    Hudgins, D. M.; Allamandola, L. J.

    1995-01-01

    Gaseous, ionized polycyclic aromatic hydrocarbons (PAHs) are thought to be responsible for a very common family of interstellar infrared emission bands. Here the near- and mid-infrared spectra of the cations of the five most thermodynamically favored PAHs up to coronene:phenanthrene, pyrene, benzo[e]pyrene, benzo[ghi]perylene, and coronene, are presented to test this hypothesis. For those molecules that have been studied previously (pyrene, pyrene-d10, and coronene), band positions and relative intensities are in agreement. In all of these cases we report additional features. Absolute integrated absorbance values are given for the phenanthrene, perdeuteriophenanthrene, pyrene, benzo[ghi]perylene, and coronene cations. With the exception of coronene, the cation bands corresponding to the CC modes are typically 2-5 times more intense than those of the CH out-of-plane bending vibrations. For the cations, the CC stretching and CH in-plane bending modes give rise to bands that are an order of magnitude stronger than those of the neutral species, and the CH out-of-plane bends produce bands that are 5-20 times weaker than those of the neutral species. This behavior is similar to that found in most other PAH cations studied to date. The astronomical implications of these PAH cation spectra are also discussed.

  2. Comparative study of charge division in substituted benzene cations

    NASA Astrophysics Data System (ADS)

    Lee, Kang Taek; Sung, Jiha; Lee, Kwang Jun; Kim, Hyung Min; Han, Kyu Young; Park, Young Dong; Kim, Seong Keun

    2007-06-01

    A recently proposed phenomenon of charge division in a molecular cation [K. T. Lee et al., J. Am. Chem. Soc. 129, 2588 (2007)] was examined in a number of molecules by experiment and theory. We investigated the spatial distribution of electrostatic charge in the cation of the following benzene derivatives: n-propylbenzene (PB), 3-phenylpropionic acid (PPA), 2-phenylethyl alcohol (PEAL), and 2-phenylethylamine (PEA). A density functional theory calculation indicated that the positive charge was divided into two cationic charge cores in both conformers of PEA+, while it is localized mainly on the phenyl group in PB+, PPA+, and PEAL+. This finding was experimentally verified by the characteristic range of electronic transition of these species reflected in the fragmentation pattern of the mass spectra. The degree of charge division in PEA+ was slightly less than in the cationic conformers of L-phenylalanine in its subgroup II. The charge distribution in a phenyl-containing cation is suggested to depend on whether there exists a functional group that can act as a competing charge core against the phenyl ring.

  3. Probing eudesmane cation-π interactions in catalysis by aristolochene synthase with non-canonical amino acids.

    PubMed

    Faraldos, Juan A; Antonczak, Alicja K; González, Verónica; Fullerton, Rebecca; Tippmann, Eric M; Allemann, Rudolf K

    2011-09-07

    Stabilization of the reaction intermediate eudesmane cation (3) through interaction with Trp 334 during catalysis by aristolochene synthase from Penicillium roqueforti was investigated by site-directed incorporation of proteinogenic and non-canonical aromatic amino acids. The amount of germacrene A (2) generated by the mutant enzymes served as a measure of the stabilization of 3. 2 is a neutral intermediate, from which 3 is formed during PR-AS catalysis by protonation of the C6,C7 double bond. The replacement of Trp 334 with para-substituted phenylalanines of increasing electron-withdrawing properties led to a progressive accumulation of 2 that showed a good correlation with the interaction energies of simple cations such as Na(+) with substituted benzenes. These results provide compelling evidence for the stabilizing role played by Trp 334 in aristolochene synthase catalysis for the energetically demanding transformation of 2 to 3.

  4. Structure-transfection activity relationships in a series of novel cationic lipids with heterocyclic head-groups.

    PubMed

    Ivanova, Ekaterina A; Maslov, Mikhail A; Kabilova, Tatyana O; Puchkov, Pavel A; Alekseeva, Anna S; Boldyrev, Ivan A; Vlassov, Valentin V; Serebrennikova, Galina A; Morozova, Nina G; Zenkova, Marina A

    2013-11-07

    Cationic liposomes are promising candidates for the delivery of various therapeutic nucleic acids. Here, we report a convenient synthesis of carbamate-type cationic lipids with various hydrophobic domains (tetradecanol, dialkylglycerol, cholesterol) and positively charged head-groups (pyridinium, N-methylimidazolium, N-methylmorpholinium) and data on the structure-transfection activity relationships. It was found that single-chain lipids possess high surface activity, which correlates with high cytotoxicity due to their ability to disrupt the cellular membrane by combined hydrophobic and electrostatic interactions. Liposomes containing these lipids also display high cytotoxicity with respect to all cell lines. Irrespective of chemical structures, all cationic lipids form liposomes with similar sizes and surface potentials. The characteristics of complexes composed of cationic liposomes and nucleic acids depend mostly on the type of nucleic acid and P/N ratios. In the case of oligodeoxyribonucleotide delivery, the transfection activity depends on the type of cationic head-group regardless of the type of hydrophobic domain: all types of cationic liposomes mediate efficient oligonucleotide transfer into 80-90% of the eukaryotic cells, and liposomes based on lipids with N-methylmorpholinium cationic head-group display the highest transfection activity. In the case of plasmid DNA and siRNA, the type of hydrophobic domain determines the transfection activity: liposomes composed of cholesterol-based lipids were the most efficient in DNA transfer, while liposomes containing glycerol-based lipids exhibited reasonable activity in siRNA delivery under serum-free conditions.

  5. Raman and IR studies and DFT calculations of the vibrational spectra of 2,4-Dithiouracil and its cation and anion

    NASA Astrophysics Data System (ADS)

    Singh, R.; Yadav, R. A.

    2014-09-01

    Raman and FTIR spectra of solid 2,4-Dithiouracil (DTU) at room temperature have been recorded. DFT calculations were carried out to compute the optimized molecular geometries, GAPT charges and fundamental vibrational frequencies along with their corresponding IR intensities, Raman activities and depolarization ratios of the Raman bands for the neutral DTU molecule and its cation (DTU+) and anion (DTU-) using the Gaussian-03 software. Addition of one electron leads to increase in the atomic charges on the sites N1 and N3 and decrease in the atomic charges on the sites S8 and S10. Due to ionization of DTU molecule, the charge at the site C6 decreases in the cationic and anionic radicals of DTU as compared to its neutral species. As a result of anionic radicalization, the C5sbnd C6 bond length increases and loses its double bond character while the C4sbnd C5 bond length decreases. In the case of the DTU+ ion the IR and Raman band corresponding to the out-of-phase coupled Nsbnd H stretching mode is strongest amongst the three species. The anionic DTU radical is found to be the most stable. The two NH out-of-plane bending modes are found to originate due to out-of-phase and in-phase coupling of the two NH bonds in the anion and cation contrary to the case of the neutral DTU molecule in which the out-of-plane bending motions of the two NH bonds are not coupled.

  6. Raman and IR studies and DFT calculations of the vibrational spectra of 2,4-Dithiouracil and its cation and anion.

    PubMed

    Singh, R; Yadav, R A

    2014-09-15

    Raman and FTIR spectra of solid 2,4-Dithiouracil (DTU) at room temperature have been recorded. DFT calculations were carried out to compute the optimized molecular geometries, GAPT charges and fundamental vibrational frequencies along with their corresponding IR intensities, Raman activities and depolarization ratios of the Raman bands for the neutral DTU molecule and its cation (DTU+) and anion (DTU-) using the Gaussian-03 software. Addition of one electron leads to increase in the atomic charges on the sites N1 and N3 and decrease in the atomic charges on the sites S8 and S10. Due to ionization of DTU molecule, the charge at the site C6 decreases in the cationic and anionic radicals of DTU as compared to its neutral species. As a result of anionic radicalization, the C5C6 bond length increases and loses its double bond character while the C4C5 bond length decreases. In the case of the DTU+ ion the IR and Raman band corresponding to the out-of-phase coupled NH stretching mode is strongest amongst the three species. The anionic DTU radical is found to be the most stable. The two NH out-of-plane bending modes are found to originate due to out-of-phase and in-phase coupling of the two NH bonds in the anion and cation contrary to the case of the neutral DTU molecule in which the out-of-plane bending motions of the two NH bonds are not coupled. Copyright © 2014 Elsevier B.V. All rights reserved.

  7. Investigation on vascular cytotoxicity and extravascular transport of cationic polymer nanoparticles using perfusable 3D microvessel model.

    PubMed

    Ahn, Jungho; Cho, Chong-Su; Cho, Seong Woo; Kang, Joo H; Kim, Sung-Yon; Min, Dal-Hee; Song, Joon Myong; Park, Tae-Eun; Jeon, Noo Li

    2018-05-25

    Vascular networks are the first sites exposed to cationic polymer nanoparticles (NPs) administered intravenously, and thus function as a barrier for NPs reaching the target organ. While cationic polymer NPs have been intensively studied as non-viral delivery systems, their biological effects in human microvessels have been poorly investigated due to a lack of appropriate in vitro systems. Here, we employed a three-dimensional microvessel on a chip, which accurately models in vivo conditions. An open and perfused microvessel surrounded by pericytes was shown to reproduce the important features of living vasculature, including barrier function and biomarkers. Using this microvessel chip, we observed contraction of the microvascular lumen induced by perfused polyethylenimine (PEI)/DNA NPs. We demonstrated that the oxidative stress present when microvessels were exposed to PEI NPs led to rearrangement of microtubules resulting in microvessel contraction. Furthermore, the transcytotic behavior of PEI NPs was analyzed in the microvessel by monitoring the escape of PEI NPs from the microvascular lumen into the perivascular region, which was not possible in two-dimensional culture systems. With our new understanding of the different behaviors of cationic polymer NPs depending on their transcytotic route, we suggest that caveolae-mediated transcytosis is a powerful route for efficient extravascular transport. Microvascular networks are not only biological system constituting largest surface area in the body and but also first site exposed to nanoparticle in vivo. While cationic polymer NPs have been intensively studied as non-viral delivery systems, its biological effects in human microvessel have been poorly investigated due to lack of appropriate in vitro systems. Here, we microengineered an open and perfused 3D pericyte incorporated microvessel model which possesses same morphological characteristic of in vivo. Using the microengineered model, this study represents the

  8. [Antioxidant activity of cationic whey protein isolate].

    PubMed

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

    2012-01-01

    The process of lipid peroxidation (LPO) in biological membranes of cells is carried out by free radical mechanism, a feature of which is the interaction of radicals with other molecules. In this work we investigated the antioxidant activity of cationic whey protein isolate, obtained by the cation-exchange chromatography on KM-cellulose from raw cow's milk, in vitro and in vivo. In biological liquids, which are milk, blood serum, fetal fluids, contains a complex of biologically active substances with a unique multifunctional properties, and which are carrying out a protective, antimicrobial, regenerating, antioxidant, immunomodulatory, regulatory and others functions. Contents of the isolate were determined electrophoretically and by its biological activity. Cationic whey protein isolate included lactoperoxidase, lactoferrin, pancreatic RNase, lysozyme and angeogenin. The given isolate significantly has an antioxidant effect in model experimental systems in vitro and therefore may be considered as a factor that can adjust the intensity of lipid oxidation. In model solutions products of lipid oxidation were obtained by oxidation of phosphatidylcholine by hydrogen peroxide in the presence of a source of iron. The composition of the reaction mixture: 0,4 mM H2O2; 50 mcM of hemin; 2 mg/ml L-alpha-phosphatidylcholine from soybean (Sigma, German). Lipid peroxidation products were formed during the incubation of the reaction mixture for two hours at 37 degrees C. In our studies rats in the adaptation period immediately after isolation from the nest obtained from food given orally native cationic whey protein isolate at the concentration three times higher than in fresh cow's milk. On the manifestation of the antioxidant activity of cationic whey protein isolate in vivo evidence decrease of lipid peroxidation products concentration in the blood of rats from the experimental group receipt whey protein isolate in dos 0,6 mg/g for more than 20% (p<0,05) with oral feeding. Thus

  9. A Scale Model of Cation Exchange for Classroom Demonstration.

    ERIC Educational Resources Information Center

    Guertal, E. A.; Hattey, J. A.

    1996-01-01

    Describes a project that developed a scale model of cation exchange that can be used for a classroom demonstration. The model uses kaolinite clay, nails, plywood, and foam balls to enable students to gain a better understanding of the exchange complex of soil clays. (DDR)

  10. Column study of Cr(VI) removal by cationic hydrogel for in-situ remediation of contaminated groundwater and soil

    NASA Astrophysics Data System (ADS)

    Tang, Samuel C. N.; Yin, Ke; Lo, Irene M. C.

    2011-07-01

    Column experiments were conducted for examining the effectiveness of the cationic hydrogel on Cr(VI) removal from groundwater and soil. For in-situ groundwater remediation, the effects of background anions, humic acid (HA) and pH were studied. Cr(VI) has a higher preference for being adsorbed onto the cationic hydrogel than sulphate, bicarbonate ions and HA. However, the adsorbed HA reduced the Cr(VI) removal capacity of the cationic hydrogel, especially after regeneration of the adsorbents, probably due to the blockage of adsorption sites. The Cr(VI) removal was slightly influenced by the groundwater pH that could be attributed to Cr(VI) speciation. The 6-cycle regeneration and reusability study shows that the effectiveness of the cationic hydrogel remained almost unchanged. On average, 93% of the adsorbed Cr(VI) was recovered in each cycle and concentrated Cr(VI) solution was obtained after regeneration. For in-situ soil remediation, the flushing water pH had an insignificant effect on the release of Cr(VI) from the soils. Multiple-pulse flushing increased the removal of Cr(VI) from the soils. In contrast, more flushing water and longer operation may be required to achieve the same removal level by continuous flushing.

  11. Effects of low-level radioactive-waste disposal on water chemistry in the unsaturated zone at a site near Sheffield, Illinois, 1982-84

    USGS Publications Warehouse

    Peters, C.A.; Striegl, Robert G.; Mills, P.C.; Healy, R.W.

    1992-01-01

    A 1982-84 field study defined the chemistry of water collected from the unsaturated zone at a low-level radioactive-waste disposal site near Sheffield, Bureau County, Ill. Chemical data were evaluated to determine the principal, naturally occurring geochemical reactions in the unsaturated zone and to evaluate waste-induced effects on pore-water chemistry. Samples of precipitation, unsaturated-zone pore water, and saturated-zone water were analyzed for specific conductance, pH, alkalinity, major cations and anions, dissolved organic carbon, gross alpha and beta radiation, and tritium. Little change in concentration of most major constituents in the unsaturated-zone water was observed with respect to depth or distance from disposal trenches. Tritium and dissolved organic carbon concentrations were, however, dependent on proximity to trenches. The primary reactions, both on-site and off-site, were carbonate and clay dissolution, cation exchange, and the oxidation of pyrite. The major difference between on-site and off-site inorganic water chemistry resulted from the removal of the Roxana Silt and the Radnor Till Member of the Glasford Formation from on-site. Off-site, the Roxana Silt contributed substantial quantities of sodium to solution from montmorillonite dissolution and associated cation-exchange reactions. The Radnor Till Member provided exchange surfaces for magnesium. Precipitation at the site had an ionic composition of calcium zinc sulfate and an average pH of 4.6. Within 0.3 meter of the land surface, infiltrating rainwater or snowmelt changed to an ionic composition of calcium sulfate off-site and calcium bicarbonate on-site and had an average pH of 7.9; below that depth, pH averaged 7.5 and the ionic composition generally was calcium magnesium bicarbonate. Alkalinity and specific conductance differed primarily according to composition of geologic materials. Tritium concentrations ranged from 0.2 (detection limit) to 1,380 nanocuries per liter. The

  12. Effects of low-level radioactive-waste disposal on water chemistry in the unsaturated zone at a site near Sheffield, Illinois, 1982-84

    USGS Publications Warehouse

    Peters, C.A.; Striegl, Robert G.; Mills, P.C.; Healy, R.W.

    1992-01-01

    A 1982-84 field study defined the chemistry of water collected from the unsaturated zone at a low-level radioactive-waste disposal site near Sheffield, Bureau County, Illinois. Chemical data were evaluated to determine the principal naturally occurring geochemical reactions in the unsaturated zone and to evaluate waste-induced effects on pore-water chemistry. Samples of precipitation, unsaturated-zone pore water, and saturated-zone water were analyzed for specific conductance, pH, alkalinity, major cations and anions, dissolved organic carbon, gross alpha and beta radiation, and tritium. Little change in concentration of most major constituents in the unsaturated-zone water was observed with respect to depth or distance from disposal trenches. Tritium and dissolved organic carbon concentrations were, however, dependent on proximity to trenches. The primary reactions, both on- site and off-site, were carbonate and clay dissolution, cation exchange, and the oxidation of pyrite. The major difference between on-site and off-site inorganic water chemistry resulted from the removal of the Roxana Silt and the Radnor Till Member of the Glasford Formation from on-site. Off-site, the Roxana Silt contributed substantial quantities of sodium to solution from montmorillonite dissolution and associated cation-exchange reactions. The Radnor Till Member provided exchange surfaces for magnesium. Precipitation at the site had an ionic composition of calcium zinc sulfate and an average pH of 4.6. Within 0.3 meter of the land surface, infiltrating rain water or snowmelt changed to an ionic canposition of calcium sulfate off-site and calcium bicarbonate on-site and had an average pH of 7.9; below that depth, pH averaged 7.5 and the ionic composition generally was calcium magnesium bicarbonate. Alkalinity and specific conductance differed primarily according to composition of geologic materials. Tritium concentrations ranged from 0.2 (detection limit) to 1,380 nanocuries per liter. The

  13. Cell-penetrating cationic siRNA and lipophilic derivatives efficient at nanomolar concentrations in the presence of serum and albumin.

    PubMed

    Perche, Phanélie; Nothisen, Marc; Bagilet, Jérémy; Behr, Jean-Paul; Kotera, Mitsuharu; Remy, Jean-Serge

    2013-08-28

    Despite its considerable interest in human therapy, in vivo siRNA delivery is still suffering from hurdles of vectorization. We have shown recently efficient gene silencing by non-vectorized cationic siRNA. Here, we describe the synthesis and in vitro evaluation of new amphiphilic cationic siRNA. C₁₂-, (C₁₂)₂- and cholesteryl-spermine(x)-siRNA were capable of luciferase knockdown at nanomolar concentrations without vectorization (i.e. one to two orders of magnitude more potent than commercially available cholesteryl siRNA). Moreover, incubation in the presence of serum did not impair their efficiency. Finally, amphiphilic cationic siRNA was pre-loaded on albumin. In A549Luc cells in the presence of serum, these siRNA conjugates were highly effective and had low toxicity. Copyright © 2013. Published by Elsevier B.V.

  14. A second component of the SltA-dependent cation tolerance pathway in Aspergillus nidulans.

    PubMed

    Mellado, Laura; Calcagno-Pizarelli, Ana Maria; Lockington, Robin A; Cortese, Marc S; Kelly, Joan M; Arst, Herbert N; Espeso, Eduardo A

    2015-09-01

    The transcriptional response to alkali metal cation stress is mediated by the zinc finger transcription factor SltA in Aspergillus nidulans and probably in other fungi of the pezizomycotina subphylum. A second component of this pathway has been identified and characterized. SltB is a 1272 amino acid protein with at least two putative functional domains, a pseudo-kinase and a serine-endoprotease, involved in signaling to the transcription factor SltA. Absence of SltB activity results in nearly identical phenotypes to those observed for a null sltA mutant. Hypersensitivity to a variety of monovalent and divalent cations, and to medium alkalinization are among the phenotypes exhibited by a null sltB mutant. Calcium homeostasis is an exception and this cation improves growth of sltΔ mutants. Moreover, loss of kinase HalA in conjunction with loss-of-function sltA or sltB mutations leads to pronounced calcium auxotrophy. sltA sltB double null mutants display a cation stress sensitive phenotype indistinguishable from that of single slt mutants showing the close functional relationship between these two proteins. This functional relationship is reinforced by the fact that numerous mutations in both slt loci can be isolated as suppressors of poor colonial growth resulting from certain null vps (vacuolar protein sorting) mutations. In addition to allowing identification of sltB, our sltB missense mutations enabled prediction of functional regions in the SltB protein. Although the relationship between the Slt and Vps pathways remains enigmatic, absence of SltB, like that of SltA, leads to vacuolar hypertrophy. Importantly, the phenotypes of selected sltA and sltB mutations demonstrate that suppression of null vps mutations is not dependent on the inability to tolerate cation stress. Thus a specific role for both SltA and SltB in the VPS pathway seems likely. Finally, it is noteworthy that SltA and SltB have a similar, limited phylogenetic distribution, being restricted to

  15. Cationic nanoemulsions as nucleic acids delivery systems.

    PubMed

    Teixeira, Helder Ferreira; Bruxel, Fernanda; Fraga, Michelle; Schuh, Roselena Silvestri; Zorzi, Giovanni Konat; Matte, Ursula; Fattal, Elias

    2017-12-20

    Since the first clinical studies, knowledge in the field of gene therapy has advanced significantly, and these advances led to the development and subsequent approval of the first gene medicines. Although viral vectors-based products offer efficient gene expression, problems related to their safety and immune response have limited their clinical use. Thus, design and optimization of nonviral vectors is presented as a promising strategy in this scenario. Nonviral systems are nanotechnology-based products composed of polymers or lipids, which are usually biodegradable and biocompatible. Cationic liposomes are the most studied nonviral carriers and knowledge about these systems has greatly evolved, especially in understanding the role of phospholipids and cationic lipids. However, the search for efficient delivery systems aiming at gene therapy remains a challenge. In this context, cationic nanoemulsions have proved to be an interesting approach, as their ability to protect and efficiently deliver nucleic acids for diverse therapeutic applications has been demonstrated. This review focused on cationic nanoemulsions designed for gene therapy, providing an overview on their composition, physicochemical properties, and their efficacy on biological response in vitro and in vivo. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Enhancing Cation Diffusion and Suppressing Anion Diffusion via Lewis-Acidic Polymer Electrolytes.

    PubMed

    Savoie, Brett M; Webb, Michael A; Miller, Thomas F

    2017-02-02

    Solid polymer electrolytes (SPEs) have the potential to increase both the energy density and stability of lithium-based batteries, but low Li + conductivity remains a barrier to technological viability. SPEs are designed to maximize Li + diffusivity relative to the anion while maintaining sufficient salt solubility. It is thus remarkable that poly(ethylene oxide) (PEO), the most widely used SPE, exhibits Li + diffusivity that is an order of magnitude smaller than that of typical counterions at moderate salt concentrations. We show that Lewis-basic polymers like PEO favor slow cation and rapid anion diffusion, while this relationship can be reversed in Lewis-acidic polymers. Using molecular dynamics, polyboranes are identified that achieve up to 10-fold increases in Li + diffusivities and significant decreases in anion diffusivities, relative to PEO in the dilute-ion regime. These results illustrate a general principle for increasing Li + diffusivity and transference number with chemistries that exhibit weaker cation and stronger anion coordination.

  17. Effect of Divalent Cation Removal on the Structure of Gram-Negative Bacterial Outer Membrane Models

    PubMed Central

    2014-01-01

    The Gram-negative bacterial outer membrane (GNB-OM) is asymmetric in its lipid composition with a phospholipid-rich inner leaflet and an outer leaflet predominantly composed of lipopolysaccharides (LPS). LPS are polyanionic molecules, with numerous phosphate groups present in the lipid A and core oligosaccharide regions. The repulsive forces due to accumulation of the negative charges are screened and bridged by the divalent cations (Mg2+ and Ca2+) that are known to be crucial for the integrity of the bacterial OM. Indeed, chelation of divalent cations is a well-established method to permeabilize Gram-negative bacteria such as Escherichia coli. Here, we use X-ray and neutron reflectivity (XRR and NR, respectively) techniques to examine the role of calcium ions in the stability of a model GNB-OM. Using XRR we show that Ca2+ binds to the core region of the rough mutant LPS (RaLPS) films, producing more ordered structures in comparison to divalent cation free monolayers. Using recently developed solid-supported models of the GNB-OM, we study the effect of calcium removal on the asymmetry of DPPC:RaLPS bilayers. We show that without the charge screening effect of divalent cations, the LPS is forced to overcome the thermodynamically unfavorable energy barrier and flip across the hydrophobic bilayer to minimize the repulsive electrostatic forces, resulting in about 20% mixing of LPS and DPPC between the inner and outer bilayer leaflets. These results reveal for the first time the molecular details behind the well-known mechanism of outer membrane stabilization by divalent cations. This confirms the relevance of the asymmetric models for future studies of outer membrane stability and antibiotic penetration. PMID:25489959

  18. Anisotropic magnetic structures of the Mn R MnSbO6 high-pressure doubly ordered perovskites (R =La , Pr, and Nd)

    NASA Astrophysics Data System (ADS)

    Solana-Madruga, Elena; Arévalo-López, Ángel M.; Dos santos-García, Antonio J.; Ritter, Clemens; Cascales, Concepción; Sáez-Puche, Regino; Attfield, J. Paul

    2018-04-01

    A new type of doubly ordered perovskite (also reported as double double perovskite, DDPv) structure combining columnar and rock-salt orders of the cations at the A and B sites, respectively, was recently found at high pressure for Mn R MnSb O6 (R =La -Sm ). Here we report further magnetic structures of these compounds. M n2 + spins align into antiparallel ferromagnetic sublattices along the x axis for MnLaMnSb O6 , while the magnetic anisotropy of P r3 + magnetic moments induces their preferential order along the z direction for MnPrMnSb O6 . The magnetic structure of MnNdMnSb O6 was reported to show a spin-reorientation transition of M n2 + spins from the z axis towards the x axis driven by the ordering of N d3 + magnetic moments. The crystal-field parameters for P r3 + and N d3 + at the 4 e C2 site of their DDPv structure have been semiempirically estimated and used to derive their energy levels and associated wave functions. The results demonstrate that the spin-reorientation transition in MnNdMnSb O6 arises as a consequence of the crystal-field-induced magnetic anisotropy of N d3 + .

  19. Application of the Aquifer Impact Model to support decisions at a CO 2 sequestration site: Modeling and Analysis: Application of the Aquifer Impact Model to support decisions at a CO 2

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

    Bacon, Diana Holford; Locke II, Randall A.; Keating, Elizabeth

    The National Risk Assessment Partnership (NRAP) has developed a suite of tools to assess and manage risk at CO2 sequestration sites (1). The NRAP tool suite includes the Aquifer Impact Model (AIM), based on reduced order models developed using site-specific data from two aquifers (alluvium and carbonate). The models accept aquifer parameters as a range of variable inputs so they may have more broad applicability. Guidelines have been developed for determining the aquifer types for which the ROMs should be applicable. This paper considers the applicability of the aquifer models in AIM to predicting the impact of CO2 or Brinemore » leakage were it to occur at the Illinois Basin Decatur Project (IBDP). Based on the results of the sensitivity analysis, the hydraulic parameters and leakage source term magnitude are more sensitive than clay fraction or cation exchange capacity. Sand permeability was the only hydraulic parameter measured at the IBDP site. More information on the other hydraulic parameters, such as sand fraction and sand/clay correlation lengths, could reduce uncertainty in risk estimates. Some non-adjustable parameters, such as the initial pH and TDS and the pH no-impact threshold, are significantly different for the ROM than for the observations at the IBDP site. The reduced order model could be made more useful to a wider range of sites if the initial conditions and no-impact threshold values were adjustable parameters.« less

  20. Studies on Cation-induced Thylakoid Membrane Stacking, Fluorescence Yield, and Photochemical Efficiency 1

    PubMed Central

    Jennings, Robert Charles; Forti, Giorgio; Gerola, Paolo Domenico; Garlaschi, Flavio Massimo

    1978-01-01

    Trypsin digestion of photosynthetic membranes isolated from spinach (Spinacia oleracea L.) leaves eliminates the cation stimulation of chlorophyll fluorescence. High concentrations of cations protect the fluorescence yield against trypsin digestion, and the cation specificity for this protection closely resembles that required for the stimulation of fluorescence by cations. Trypsin digestion reverses cation-induced thylakoid stacking, and the time course of this effect seems to parallel that of the reversal of cation fluorescence. High concentrations of cations protect thylakoid stacking and cation-stimulated fluorescence alike. The cation stimulation of photosytem II photochemistry remains intact after trypsinization has reversed both cation-induced thylakoid stacking and fluorescence yield. It is concluded that cation-stimulated fluorescence yield, and not the cation stimulation of photosystem II photochemistry, is associated with thylakoid membrane stacking. ImagesFig. 2Fig. 3 PMID:16660630