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Sample records for cgmp-activated cation conductance

  1. Cation Defects and Conductivity in Transparent Oxides

    SciTech Connect

    Exarhos, Gregory J.; Windisch, Charles F.; Ferris, Kim F.; Owings, Robert R.

    2007-10-24

    High quality doped zinc oxide and mixed transition metal spinel oxide films have been deposited by means of sputter deposition from metal and metal oxide targets, and by spin casting from aqueous or alcoholic precursor solutions. Deposition conditions and post-deposition processing are found to alter cation oxidation states and their distributions in both oxide materials resulting in marked changes to both optical transmission and electrical response. For ZnO, partial reduction of the neat or doped material by hydrogen treatment of the heated film or by electrochemical processing renders the oxide n-type conducting. Continued reduction was found to diminish conductivity. In contrast, oxidation of the infrared transparent p-type spinel conductors typified by NiCo2O4 was found to increase conductivity. The disparate behavior of these two materials is caused in part by the sign of the charge carrier and by the existence of two different charge transport mechanisms that are identified as free carrier conduction and polaron hopping. While much work has been reported concerning structure/property relationships in the free carrier conducting oxides, there is a significantly smaller body of information on transparent polaron conductors. In this paper, we identify key parameters that promote conductivity in mixed metal spinel oxides and compare their behavior with that of the free carrier TCO’s.

  2. Lithium-cation conductivity and crystal structure of lithium diphosphate

    SciTech Connect

    Voronin, V.I.; Sherstobitova, E.A.; Blatov, V.A.; Shekhtman, G.Sh.

    2014-03-15

    The electrical conductivity of lithium diphosphate Li{sub 4}P{sub 2}O{sub 7} has been measured and jump-like increasing of ionic conductivity at 913 K has been found. The crystal structure of Li{sub 4}P{sub 2}O{sub 7} has been refined using high temperature neutron diffraction at 300–1050 K. At 913 K low temperature triclinic form of Li{sub 4}P{sub 2}O{sub 7} transforms into high temperature monoclinic one, space group P2{sub 1}/n, a=8.8261(4) Å, b=5.2028(4) Å, c=13.3119(2) Å, β=104.372(6)°. The migration maps of Li{sup +} cations based on experimental data implemented into program package TOPOS have been explored. It was found that lithium cations in both low- and high temperature forms of Li{sub 4}P{sub 2}O{sub 7} migrate in three dimensions. Cross sections of the migrations channels extend as the temperature rises, but at the phase transition point have a sharp growth showing a strong “crystal structure – ion conductivity” correlation. -- Graphical abstract: Crystal structure of Li{sub 4}P{sub 2}O{sub 7} at 950 K. Red balls represent oxygen atoms; black lines show Li{sup +} ion migration channels in the layers perpendicular to [001] direction. Highlights: • Structure of Li{sub 4}P{sub 2}O{sub 7} has been refined using high temperature neutron diffraction. • At 913 K triclinic form of Li{sub 4}P{sub 2}O{sub 7} transforms into high temperature monoclinic one. • The migration maps of Li{sup +} implemented into program package TOPOS have been explored. • Cross sections of the migrations channels at the phase transition have a sharp growth.

  3. Molecular mobility and cation conduction in sulfonated polyester copolymer ionomers

    NASA Astrophysics Data System (ADS)

    Tudryn, Gregory; King, Daniel; O'Reilly, Michael; Winey, Karen; Colby, Ralph

    2011-03-01

    Poly(ethylene oxide) ionomers are candidate materials for electrolytes in energy storage devices due to the ability of ether oxygen to solvate cations. Copolyester ionomers are synthesized via condensation of sulfonated phthalates with mixtures of PEG and PTMG to make random copolymer ionomers with identical ion content. Variation of the PEG/PTMG composition changes Tg, dielectric constant and ionic aggregation; each with consequences for ion transport. Dielectric spectroscopy is used to determine number density of conducting ions, their mobility and extent of aggregation. Conductivity and mobility show Vogel temperature dependence and increase with PEG content; even though PTMG ionomers have lower Tg. Conducting ion densities show Arrhenius temperature dependence and are nearly identical for polymers containing PEG. SAXS confirms the extent of aggregation and temperature response from dielectric results, and exposes phase separation as PTMG content is increased. The tradeoff between ion-solvation and low Tg in this study provides fundamental understanding of ionic aggregation and ion transport in polymer electrolytes.

  4. The natural tiling approach to cation conductivity in KAlO2 polymorphs.

    PubMed

    Voronin, Vladimir I; Shekhtman, Georgi Sh; Blatov, Vladislav A

    2012-08-01

    A detailed analysis of correlations between structural features and cation conductivity is performed for KAlO(2) polymorphs in a wide temperature range of 300-1023 K. To explore the migration maps of K(+) cations we have used neutron diffraction data for low- and high-temperature KAlO(2) polymorphs and applied for the first time a novel algorithm based on the natural tiling concept and implemented it into the program package TOPOS. Five independent elementary channels for the K(+) cation migration have been revealed whose cross-sections were found to be essentially different in the low-temperature form, indicating a high anisotropy of the cation conductivity. During the transition to the cubic high-temperature phase all five channels become equivalent with sharply increased cross-sections that account for the jump-like increase of the cation conductivity and gives rise to its three-dimensional character. PMID:22810905

  5. Cationic Covalent Organic Frameworks: A Simple Platform of Anionic Exchange for Porosity Tuning and Proton Conduction.

    PubMed

    Ma, Heping; Liu, Bailing; Li, Bin; Zhang, Liming; Li, Yang-Guang; Tan, Hua-Qiao; Zang, Hong-Ying; Zhu, Guangshan

    2016-05-11

    Mimicking proton conduction mechanism of Nafion to construct novel proton-conducting materials with low cost and high proton conductivity is of wide interest. Herein, we have designed and synthesized a cationic covalent organic framework with high thermal and chemical stability by combining a cationic monomer, ethidium bromide (EB) (3,8-diamino-5-ethyl-6-phenylphenanthridinium bromide), with 1,3,5-triformylphloroglucinol (TFP) in Schiff base reactions. This is the first time that the stable cationic crystalline frameworks allowed for the fabrication of a series of charged COFs (EB-COF:X, X = F, Cl, Br, I) through ion exchange processes. Exchange of the extra framework ions can finely modulate the COFs' porosity and pore sizes at nanoscale. More importantly, by introducing PW12O40(3-) into this porous cationic framework, we can greatly enhance the proton conductivity of ionic COF-based material. To the best of our knowledge, EB-COF:PW12 shows the best proton conductivity at room temperature among ever reported porous organic materials. PMID:27094048

  6. A calcium-permeable cGMP-activated cation conductance in hippocampal neurons

    NASA Technical Reports Server (NTRS)

    Leinders-Zufall, T.; Rosenboom, H.; Barnstable, C. J.; Shepherd, G. M.; Zufall, F.

    1995-01-01

    Whole-cell patch clamp recordings detected a previously unidentified cGMP-activated membrane conductance in cultured rat hippocampal neurons. This conductance is nonselectively permeable for cations and is completely but reversibly blocked by external Cd2+. The Ca2+ permeability of the hippocampal cGMP-activated conductance was examined in detail, indicating that the underlying ion channels display a high relative permeability for Ca2+. The results indicate that hippocampal neurons contain a cGMP-activated membrane conductance that has some properties similar to the cyclic nucleotide-gated channels previously shown in sensory receptor cells and retinal neurons. In hippocampal neurons this conductance similarly could mediate membrane depolarization and Ca2+ fluxes in response to intracellular cGMP elevation.

  7. Ionic charge transport between blockages: Sodium cation conduction in freshly excised bulk brain tissue

    NASA Astrophysics Data System (ADS)

    Emin, David; Akhtari, Massoud; Ellingson, B. M.; Mathern, G. W.

    2015-08-01

    We analyze the transient-dc and frequency-dependent electrical conductivities between blocking electrodes. We extend this analysis to measurements of ions' transport in freshly excised bulk samples of human brain tissue whose complex cellular structure produces blockages. The associated ionic charge-carrier density and diffusivity are consistent with local values for sodium cations determined non-invasively in brain tissue by MRI (NMR) and diffusion-MRI (spin-echo NMR). The characteristic separation between blockages, about 450 microns, is very much shorter than that found for sodium-doped gel proxies for brain tissue, >1 cm.

  8. Ionic charge transport between blockages: Sodium cation conduction in freshly excised bulk brain tissue

    SciTech Connect

    Emin, David; Akhtari, Massoud; Ellingson, B. M.; Mathern, G. W.

    2015-08-15

    We analyze the transient-dc and frequency-dependent electrical conductivities between blocking electrodes. We extend this analysis to measurements of ions’ transport in freshly excised bulk samples of human brain tissue whose complex cellular structure produces blockages. The associated ionic charge-carrier density and diffusivity are consistent with local values for sodium cations determined non-invasively in brain tissue by MRI (NMR) and diffusion-MRI (spin-echo NMR). The characteristic separation between blockages, about 450 microns, is very much shorter than that found for sodium-doped gel proxies for brain tissue, >1 cm.

  9. Incorporation in lipid bilayers of a large conductance cationic channel from mitochondrial membranes.

    PubMed Central

    Thieffry, M; Chich, J F; Goldschmidt, D; Henry, J P

    1988-01-01

    Membranes from subcellular fractions of adrenal medulla were incorporated in phospholipid bilayers formed at the tip of microelectrodes. Current fluctuations recorded in the presence of a transmembrane potential revealed the existence of a voltage-dependent channel of large conductance. This channel is characterized by fast kinetics and four conductance levels separated by jumps of 100, 220 and 220 pS in 150 mM NaCl. It is permeant to Na+,K+, tetraethylammonium, Cl- and acetate and has some cation selectivity. Exposure to trypsin or pronase abolished the voltage-dependence. Upon subcellular fractionation, the activity was found to be associated with mitochondria. A similar activity was observed in mitochondrial fractions from other organs. By its kinetics, its selectivity and its potential-dependence, this channel differs from the voltage-dependent anion channel of outer mitochondrial membranes. Images PMID:2457497

  10. Preparation of metallic cation conducting polymers based on sterically hindered phenols containing polymeric systems

    DOEpatents

    Skotheim, T.A.; Okamoto, Yoshiyuki; Lee, H.S.

    1989-11-21

    The present invention relates to ion-conducting solvent-free polymeric systems characterized as being cationic single ion conductors. The solvent-free polymer electrolytes comprise a flexible polymer backbone to which is attached a metal salt, such as a lithium, sodium or potassium salt, of a sterically hindered phenol. The solid polymer electrolyte may be prepared either by (1) attaching the hindered phenol directly to a flexible polymeric backbone, followed by neutralization of the phenolic OH's or (2) reacting the hindered phenol with a polymer precursor which is then polymerized to form a flexible polymer having phenolic OH's which are subsequently neutralized. Preferably the hindered phenol-modified polymeric backbone contains a polyether segment. The ionic conductivity of these solvent-free polymer electrolytes has been measured to be in the range of 10[sup [minus]4] to 10[sup [minus]7] S cm[sup [minus]1] at room temperature.

  11. Preparation of metallic cation conducting polymers based on sterically hindered phenols containing polymeric systems

    DOEpatents

    Skotheim, Terje A.; Okamoto, Yoshiyuki; Lee, Hung S.

    1989-01-01

    The present invention relates to ion-conducting solvent-free polymeric systems characterized as being cationic single ion conductors. The solvent-free polymer electrolytes comprise a flexible polymer backbone to which is attached a metal salt, such as a lithium, sodium or potassium salt, of a sterically hindered phenol. The solid polymer electrolyte may be prepared either by (1) attaching the hindered phenol directly to a flexible polymeric backbone, followed by neutralization of the phenolic OH's or (2) reacting the hindered phenol with a polymer precursor which is then polymerized to form a flexible polymer having phenolic OH's which are subsequently neutralized. Preferably the hindered phenol-modified polymeric backbone contains a polyether segment. The ionic conductivity of these solvent-free polymer electrolytes has been measured to be in the range of 10.sup.-4 to 10.sup.-7 S cm.sup.-1 at room temperature.

  12. 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.

  13. Purinergic regulation of cation conductances and intracellular Ca2+ in cultured rat retinal pigment epithelial cells

    PubMed Central

    Ryan, Jennifer S; Baldridge, William H; Kelly, Melanie E M

    1999-01-01

    We used whole-cell patch clamp and fluorescent calcium imaging techniques to investigate the effects of adenosine 5′-triphosphate (ATP) on membrane currents and intracellular calcium concentration ([Ca2+]i)in rat retinal pigment epithelial (RPE) cells. In 62 % of RPE cells, application of 100 μM ATP elicited a fast inward current at negative membrane potentials. In 38 % of RPE cells recorded, a biphasic response to ATP was observed in which activation of the fast inward current was followed by activation of a delayed outward current. The ATP-activated inward current was a non-selective cation (NSC) current that showed inward rectification, reversed at −1.5 ± 1 mV and was permeable to monovalent cations. The NSC current was insensitive to the P2 purinoceptor antagonists, suramin or PPADS but was activated by the purinoceptor agonists UTP, ADP and 2MeSATP. The outward current activated by ATP reversed at −68 ± 3 mV (equilibrium potential for potassium (EK) = −84 mV) and was blocked by Ba2+ ions, consistent with the activation of a K+ conductance. The outward K+ conductance was also reduced by the maxi-KCa channel blocker iberiotoxin (IbTX; 10 nM), suggesting that ATP activated an outward Ca2+-activated K+ channel in rat RPE cells. The Ca2+-activated K+ current (IK(Ca)) was also activated by the purinoceptor agonists UTP, ADP and 2MeSATP. In fluo-3 or fluo-4 loaded RPE cells, ATP and the pyrimidine agonist UTP elevated [Ca2+]i. The increase in Ca2+ was not dependent on extracellular Ca2+ influx, but was sensitive to the Ca2+-ATPase inhibitor thapsigargin, confirming the involvement of intracellular Ca2+ stores release. These results suggest that rat RPE cells express both P2X purinoceptors that gate activation of a non-selective cation conductance and G protein-coupled P2Y purinoceptors that mediate Ca2+ release from intracellular stores and activation of a calcium-activated K+ current. PMID:10545141

  14. Purinergic regulation of cation conductances and intracellular Ca2+ in cultured rat retinal pigment epithelial cells.

    PubMed

    Ryan, J S; Baldridge, W H; Kelly, M E

    1999-11-01

    1. We used whole-cell patch clamp and fluorescent calcium imaging techniques to investigate the effects of adenosine 5'-triphosphate (ATP) on membrane currents and intracellular calcium concentration ([Ca2+]i)in rat retinal pigment epithelial (RPE) cells. In 62 % of RPE cells, application of 100 microM ATP elicited a fast inward current at negative membrane potentials. In 38 % of RPE cells recorded, a biphasic response to ATP was observed in which activation of the fast inward current was followed by activation of a delayed outward current. 2. The ATP-activated inward current was a non-selective cation (NSC) current that showed inward rectification, reversed at -1.5 +/- 1 mV and was permeable to monovalent cations. The NSC current was insensitive to the P2 purinoceptor antagonists, suramin or PPADS but was activated by the purinoceptor agonists UTP, ADP and 2MeSATP. 3. The outward current activated by ATP reversed at -68 +/- 3 mV (equilibrium potential for potassium (EK) = -84 mV) and was blocked by Ba2+ ions, consistent with the activation of a K+ conductance. The outward K+ conductance was also reduced by the maxi-KCa channel blocker iberiotoxin (IbTX; 10 nM), suggesting that ATP activated an outward Ca2+-activated K+ channel in rat RPE cells. The Ca2+-activated K+ current (IK(Ca)) was also activated by the purinoceptor agonists UTP, ADP and 2MeSATP. 4. In fluo-3 or fluo-4 loaded RPE cells, ATP and the pyrimidine agonist UTP elevated [Ca2+]i. The increase in Ca2+ was not dependent on extracellular Ca2+ influx, but was sensitive to the Ca2+-ATPase inhibitor thapsigargin, confirming the involvement of intracellular Ca2+ stores release. 5. These results suggest that rat RPE cells express both P2X purinoceptors that gate activation of a non-selective cation conductance and G protein-coupled P2Y purinoceptors that mediate Ca2+ release from intracellular stores and activation of a calcium-activated K+ current. PMID:10545141

  15. Highly conducting divalent Mg2+ cation solid electrolytes with well-ordered three-dimensional network structure

    NASA Astrophysics Data System (ADS)

    Tamura, Shinji; Yamane, Megumi; Hoshino, Yasunori; Imanaka, Nobuhito

    2016-03-01

    A three-dimensionally well-ordered NASICON-type Mg2+ cation conductor, (MgxHf1-x)4/(4-2x)Nb(PO4)3, was firstly developed by partial substitution of lower valent Mg2+ cation onto the Hf4+ sites in a HfNb(PO4)3 solid to realize high Mg2+ cation conductivity even at moderate temperatures. Due to the formation of well-ordered NASICON-type structure, both the high Mg2+ cation conductivity below 450 °C and the low activation energy for Mg2+ cation migration was successfully realized for the (Mg0.1Hf0.9)4/3.8Nb(PO4)3 solid. Pure Mg2+ cation conduction in the NASICON-type (Mg0.1Hf0.9)4/3.8Nb(PO4)3 solid was directly and quantitatively demonstrated by means of two kinds of dc electrolysis.

  16. Single-Crystal X-ray Structures of conductive π-Stacking Dimers of Tetrakis(alkylthio)benzene Radical Cations.

    PubMed

    Chen, Xiaoyu; Gao, Feng; Yang, Wuqin

    2016-01-01

    Salts containing radical cations of 1,2,4,5-tetrakis(isopropylthio)benzene (TPB) and 1,2,4,5-tetrakis(ethylthio) benzene (TEB) have been successfully synthesized with . These newly synthesized salts have been characterized by UV-Vis absorption, EPR spectroscopy, conductivity measurement, single crystal X-ray diffraction analysis as well as DFT calculation. This study raises the first crystal structure of conductive π-stacking radical cation with single phenyl ring and reveals their conductivity has relationship with the stack structure which affected by the substituent. PMID:27403720

  17. Single-Crystal X-ray Structures of conductive π-Stacking Dimers of Tetrakis(alkylthio)benzene Radical Cations

    PubMed Central

    Chen, Xiaoyu; Gao, Feng; Yang, Wuqin

    2016-01-01

    Salts containing radical cations of 1,2,4,5-tetrakis(isopropylthio)benzene (TPB) and 1,2,4,5-tetrakis(ethylthio) benzene (TEB) have been successfully synthesized with . These newly synthesized salts have been characterized by UV-Vis absorption, EPR spectroscopy, conductivity measurement, single crystal X-ray diffraction analysis as well as DFT calculation. This study raises the first crystal structure of conductive π-stacking radical cation with single phenyl ring and reveals their conductivity has relationship with the stack structure which affected by the substituent. PMID:27403720

  18. Single-Crystal X-ray Structures of conductive π-Stacking Dimers of Tetrakis(alkylthio)benzene Radical Cations

    NASA Astrophysics Data System (ADS)

    Chen, Xiaoyu; Gao, Feng; Yang, Wuqin

    2016-07-01

    Salts containing radical cations of 1,2,4,5-tetrakis(isopropylthio)benzene (TPB) and 1,2,4,5-tetrakis(ethylthio) benzene (TEB) have been successfully synthesized with . These newly synthesized salts have been characterized by UV-Vis absorption, EPR spectroscopy, conductivity measurement, single crystal X-ray diffraction analysis as well as DFT calculation. This study raises the first crystal structure of conductive π-stacking radical cation with single phenyl ring and reveals their conductivity has relationship with the stack structure which affected by the substituent.

  19. Characterization of cationic copolymers by capillary electrophoresis using indirect UV detection and contactless conductivity detection.

    PubMed

    Anik, Nadia; Airiau, Marc; Labeau, Marie-Pierre; Vuong, Chi-Thanh; Cottet, Hervé

    2012-01-01

    For many industrial applications, the combination of two different monomers in statistical or diblock copolymers enhances the properties of the corresponding polymer. However, during the polymerization reaction, homopolymers might be formed and can influence the properties for the applications. Consequently, the separation and the quantification of the homopolymers contained in copolymer samples are crucial. In addition, the charge density distribution of the statistical copolymer is an important characteristic for the applications. The purpose of this work was to study the characterization of a statistical copolymer of acrylic acid (AA) and diallyldimethyl ammonium chloride (DADMAC) by capillary electrophoresis (CE) in acidic conditions (cationic copolymers). For that purpose, a free solution electrophoretic separation was carried out according to the charge rate (chemical composition) independently of the molar mass. The second objective was to compare contactless conductivity detection and indirect UV absorbance modes for the quantification of DADMAC homopolymers present in copolymer samples. Different coated capillaries based on neutral or positively charged modification were also compared. The comparison of indirect absorbance UV and contactless conductimetric detection demonstrated that both detection modes can be used for a complete CE characterization of non-UV absorbing PAA-DADMAC copolymers. PMID:22169192

  20. Electrochemical cell including a solid electrolyte made from a cation conductive vitreous compound

    SciTech Connect

    Duchange, J.P.; Gabano, J.P.

    1984-04-24

    An electrochemical cell having a lithium based negative active material, an electrolyte in the form of a vitreous cation conductive compound having a formula: aP/sub 2/S/sub 5/, bLi/sub 2/S, cLiX, where X stands for chlorine, bromine or iodine, and a, b, and c are numbers chosen in such a manner that b/(a+b) lies in the range 0.61 to 0.70 and c/(a+b+c) is less than or equal to the maximum solubility in the vitreous phase of LiX in the compound aP/sub 2/S/sub 5/, bLi/sub 2/S, and a positive active material in the form of a compressed powder with particles of the electrolyte dispersed throughout said positive active material. The positive active material is chosen from the group constituted by: (CH /SUB x/ ; Cu /SUB d/ O(PO/sub 4/)/sub 2/; V/sub 6/O/sub 13/; V/sub 2/S/sub 5/; MoS/sub 3/; CuS; S; CuO; Cu/sub 3/B/sub 2/O/sub 6/; FeS/sub 2/; Pb/sub 3/O/sub 4/; Bi/sub 2/O/sub 3/; PbO; BiO(CrO/sub 4/)/sub 2/; AgBi(CrO/sub 4/)/sub 2/; I/sub 2/; MoO/sub 3/; WO/sub 3/; TiS/sub 2/; NiPS/sub 3/; copper bismuthate; and lead bismuthate.

  1. Depletion of intracellular calcium stores activates a calcium conducting nonselective cation current in mouse pancreatic acinar cells.

    PubMed

    Krause, E; Pfeiffer, F; Schmid, A; Schulz, I

    1996-12-20

    Receptor-mediated Ca2+ release from inositol (1,4,5)-trisphosphate (IP3)-sensitive Ca2+ stores causes "capacitative calcium entry" in many cell types (Putney, J. W., Jr. (1986) Cell Calcium 7, 1-12; Putney, J. W., Jr. (1990) Cell Calcium 11, 611-624). We used patch-clamp and fluorescence techniques in isolated mouse pancreatic acinar cells to identify ion currents and cytosolic calcium concentrations under conditions in which intracellular Ca2+ stores were emptied. We found that depletion of Ca2+ stores activated a calcium-release-activated nonselective cation current (ICRANC) which did not discriminate between monovalent cations. ICRANC possessed a significant conductance for Ca2+ and Ba2+. It was not inhibited by La3+, Gd3+, Co2+, or Cd2+ but was completely abolished by flufenamic acid or genistein. In whole cell and cell-attached recordings, a 40-45 pS nonselective cation channel was identified which was activated by Ca2+ store depletion. Calcium entry as detected by single cell fluorescence measurements with fluo-3 or fura-2, showed the same pharmacological properties as ICRANC. We conclude that in mouse pancreatic acinar cells 40-45 pS nonselective cation channels serve as a pathway for capacitative Ca2+ entry. This entry pathway differs from the previously described ICRAC (Hoth, M., and Penner, R. (1992) Nature 355, 353-356) in its ion-selectivity, pharmacological profile, and single-channel conductance. PMID:8955076

  2. DFT studies of all fluorothiophenes and their cations as candidate monomers for conductive polymers

    SciTech Connect

    Shirani, Hossein; Jameh-Bozorghi, Saeed; Yousefi, Ali

    2015-01-22

    In this paper, electronic, structural, and properties of mono-, di-, tri-, and tetrafluorothiophenes and their radical cations are studied using the density functional theory and B3LYP method with 6-311++G** basis set. Also, the effects of the number and position of the substituent of fluorine atoms on the properties of the thiophene ring have been studied using optimized structures obtained for these molecules and their radical cations; vibrational frequencies, spin-density distribution, size and direction of the dipole moment vector, ionization potential, electric Polarizabilities, HOMO–LUMO gaps and NICS values of these compounds have been calculated and analyzed.

  3. The Conducting Spin-Crossover Compound Combining Fe(II) Cation Complex with TCNQ in a Fractional Reduction State.

    PubMed

    Shvachko, Yuri N; Starichenko, Denis V; Korolyov, Aleksander V; Yagubskii, Eduard B; Kotov, Alexander I; Buravov, Lev I; Lyssenko, Konstantin A; Zverev, Vladimir N; Simonov, Sergey V; Zorina, Leokadiya V; Shakirova, Olga G; Lavrenova, Lyudmila G

    2016-09-01

    The radical anion salt [Fe{HC(pz)3}2](TCNQ)3 demonstrates conductivity and spin-crossover (SCO) transition associated with Fe(II) complex cation subsystem. It was synthesized and structurally characterized at temperatures 100, 300, 400, and 450 K. The compound demonstrates unusual for 7,7,8,8,-tetracyanoquinodimethane (TCNQ)-based salts quasi-two-dimensional conductivity. Pronounced changes of the in-plane direct-current resistivity and intensity of the electron paramagnetic resonance (EPR) signal, originated from TCNQ subsystem, precede the SCO transition at the midpoint T* = 445 K. The boltzmannian growth of the total magnetic response and structural changes in the vicinity of T* uniquely show that half [Fe{HC(pz)3}2] cations exist in high-spin state. Robust broadening of the EPR signal triggered by the SCO transition is interpreted in terms of cross relaxation between the TCNQ and Fe(II) spin subsystems. PMID:27541570

  4. Integration of a contactless conductivity detector into a commercial capillary cassette. Detection of inorganic cations and catecholamines.

    PubMed

    Vuorinen, Pasi S; Jussila, Matti; Sirén, Heli; Palonen, Sami; Riekkola, Marja-Liisa

    2003-03-21

    A contactless conductivity detector integrated into the capillary cassette of Agilent (3D)CE equipment is described. The detector is user-friendly, compact and easily modified. The UV detector of the (3D)CE equipment is available parallel with the contactless conductivity detector increasing the detection power. Two electrolyte solutions, 2-(N-morpholino)ethanesulfonic acid-histidine solution (20 mM, pH 6.0) and ammonium acetate (10 mM, pH 4.0), were used as the separation media for inorganic cations and organic catecholamines, respectively. The detection limit for all metal cations except barium was under 0.5 mg/l, and that for four catecholamines was ca. 10 mg/l. This last value was the same order of magnitude as achieved with parallel UV detection. PMID:12685582

  5. DC conductivity, cationic exchange capacity, and specific surface area related to chemical composition of pore lining chlorites.

    PubMed

    Henn, François; Durand, Claudine; Cerepi, Adrian; Brosse, Etienne; Giuntini, J C

    2007-07-15

    Low resistivity in argillaceous sandstone reservoirs may be attributed either to the effect of microporosity, or to specific effects due to intrinsic clays' conducting properties or to other conducting minerals. In order to distinguish these effects, cation exchange capacity, specific surface areas, and dc conductivity of various pore lining chlorite-bearing sandstones from different hydrocarbon reservoir measurements are investigated. Cation exchange capacity and specific surface area are measured on whole rocks as well as on size-separated fractions. Both sets of values are low, in agreement with the structural and textural observations. The conductivity of these chlorites, measured in air conditions and after dehydration, is investigated by means of complex impedance spectroscopy on size-separated fractions as a function of temperature and compared to that of reference clays. The results show a large influence of moisture, applied electric field frequency, and temperature on the electrical properties. The magnitude of the dehydrated clays' conductivity is such that its influence on the conductivity of argillaceous sandstone is lower than that related to the presence of water or brine by several orders of magnitude. The dc conductivity and the related activation energy of the dehydrated samples appear to be related to the chemical composition of the clays. More specifically, a clear correlation occurs with the electrical charges of the clay network, that is to say with the location, i.e., tetrahedral or octahedral sites, of the substituting trivalent elements. PMID:17433348

  6. Large tetraalkyl ammonium cations produce a reduced conductance state in the sheep cardiac sarcoplasmic reticulum Ca(2+)-release channel.

    PubMed Central

    Tinker, A; Lindsay, A R; Williams, A J

    1992-01-01

    The purified Ca(2+)-release/ryanodine receptor channel of the sheep cardiac muscle sarcoplasmic reticulum (SR) functions as a calcium-activated cation-selective channel under voltage clamp conditions following reconstitution into planar phospholipid bilayers. We have investigated the effect of large tetraalkyl ammonium (TAA) cations, (CnH2n+1)4N+ (n = 4 and 5) on monovalent cation conduction. These cations modify the conductance of the receptor channel at positive holding potentials from the cytosolic side of the channel. Under these conditions, openings are resolved as a mixture of normal full amplitude events and events of reduced conductance. The amplitude of the reduced conductance state is a fixed proportion of the normal open state. As a proportion of all open events, the occurrence of the tetrabutyl ammonium (TBA+) related subconductance state increases with concentration and increasingly positive holding potential. The TBA+ related subconductance state displays similar conduction properties to the unmodified channel; with a linear current-voltage relationship, a similar affinity for K+ and voltage-dependent block by TEA+. A method was used to quantify the voltage dependence of the occurrence of the TBA+ effect, which yielded an effective gating charge of 1.66. A second method based on kinetic analysis of the voltage dependence of transitions between the full open state and the TBA+ related subconductance state produced a similar value. In addition, this analysis revealed that the bulk of the voltage-dependence resided in the off rate. TBA+ related subconductance events, expressed as a proportion of all open events, saturated with increasing TBA+ concentration. Kinetic analysis revealed that this could be entirely accounted for by changes in the on rate. Tetrapentyl ammonium (TPeA+) causes a qualitatively similar effect with a subconductance state of lower amplitude. The voltage-dependence of the effect was comparable to that displayed by TBA+. These

  7. Research for preparation of cation-conducting solids by high-pressure synthesis and other methods

    NASA Technical Reports Server (NTRS)

    Goodenough, J. B.; Hong, H. Y. P.; Kafalas, J. A.; Dwight, K., Jr.

    1975-01-01

    It was shown that two body-centered-cubic skeleton structures, the Im3 KSbO3 phase and the defect-pyrochlore phase A(+)B2X6, do exhibit fast Na(+)-ion transport. The placement of anions at the tunnel intersection sites does not impede Na(+)-ion transport in (NaSb)3)(1/6 NaF), and may not in (Na(1+2x)Ta2 5F)(Ox). The activation energies are higher than those found in beta-alumina. There are two possible explanations for the higher activation energy: breathing of the bottleneck (site face or edge) through which the A(+) ions must pass on jumping from one site to another may be easier in a layer structure and/or A(+)-O bonding may be stronger in the cubic structures because the O(2-) ion bonds with two (instead of three) cations of the skeleton. If the former explanation is dominant, a lower activation energy may be achieved by optimizing the lattice parameter. If the latter is dominant, a new structural principle may have to be explored.

  8. Integrating high electrical conductivity and photocatalytic activity in cotton fabric by cationizing for enriched coating of negatively charged graphene oxide.

    PubMed

    Sahito, Iftikhar Ali; Sun, Kyung Chul; Arbab, Alvira Ayoub; Qadir, Muhammad Bilal; Jeong, Sung Hoon

    2015-10-01

    Electroconductive textiles have attended tremendous focus recently and researchers are making efforts to increase conductivity of e-textiles, in order to increase the use of such flexible and low cost textile materials. In this study, surface conductivity and photo catalytic activity of standard cotton fabric (SCF) was enhanced by modifying its surface charge, from negative to positive, using Bovine Serum Albumin (BSA) as a cationic agent, to convert it into cationised cotton fabric (CCF). Then, both types of fabrics were dip coated with a simple dip and dry technique for the adsorption of negatively charged graphene oxide (GO) sheets onto its surface. This resulted in 67.74% higher loading amount of GO on the CCF making self-assembly. Finally, this coating was chemically converted by vapor reduction using hydrazine hydrate to reduced graphene oxide (rGO) for restoration of a high electrical conductivity at the fabric surface. Our results revealed that with such high loading of GO, the surface resistance of CCF was only 40Ω/sq as compared to 510Ω/sq of the SCF and a 66% higher photo catalytic activity was also achieved through cationization for improved GO coating. Graphene coated SCF and CCF were characterized using FE-SEM, FTIR, Raman, UV-vis, WAXD, EDX and XPS spectroscopy to ascertain successful reduction of GO to rGO. The effect of BSA treatment on adsorption of cotton fabric was studied using drop shape analyzer to measure contact angle and for thermal and mechanical resistance, the fabric was tested for TGA and tensile strength, respectively. rGO coated fabric also showed slightly improved thermal stability yet a minor loss of strength was observed. The high flexibility, photocatalytic activity and excellent conductivity of this fabric suggests that it can be used as an electrode material for various applications. PMID:26076630

  9. An evaluation of soluble cations and anions on the conductivity and rate of flocculation of kaolins

    NASA Astrophysics Data System (ADS)

    Fulton, Deborah Lee

    1998-10-01

    The focus of this project was to learn how ionic concentrations and their contributions to electric conductivity influence the flocculation behavior of kaolin/water suspensions. Sodium silicate, calcium chloride, and magnesium sulfate were used as chemical additives. The specific surface areas, particle size distributions, and methylene blue indices for two kaolins were measured. The SSA and MBI for these kaolins indicated that they possessed inherent differences in SSA and flocculation behaviors. Rheological studies were also performed. Testing included simultaneous gelation, deflocculation, and pH tests. Viscosity, pH, temperature, and chemical additive concentrations were monitored at each point. Testing was performed at 45/55 wt% solids. Effects of additions of various levels of deflocculant and flocculant to each of the kaolin/water suspensions were studied by making several suspensions from each kaolin. The concentrations of dispersant, and flocculant levels and types were varied to produce suspensions with different chemical additive "histories," but all with similar final apparent viscosities. Slurry filtrates were analyzed for conductivity, pH, temperature, and ion concentrations of (Al3+, Fe2+,3+, Ca 2+, Mg+, Na+, SO4 2--, and Cl--). Plastic properties were calculated to determine how variations in suspension histories affected conductivities, pH, and detectable ion contents of the suspensions. These analyses were performed on starting slurries which were under-, completely-, and over-deflocculated before further additions of flocculants and deflocculant were added to tune the slurries to the final, constant, target viscosity. Results showed that rates of flocculation and conductivities increased as concentrations of ions increased. By increasing conductivity correlations with increases in flocculation occurs, which yields higher rates of buildup, or RBU [1]. This is the single most important slip control property in the whitewares industry. Shear

  10. D2-like dopamine receptors depolarize dorsal raphe serotonin neurons through the activation of nonselective cationic conductance.

    PubMed

    Aman, Teresa K; Shen, Roh-Yu; Haj-Dahmane, Samir

    2007-01-01

    The dorsal raphe (DR) receives a prominent dopamine (DA) input that has been suggested to play a key role in the regulation of central serotoninergic transmission. DA is known to directly depolarize DR serotonin neurons, but the underlying mechanisms are not well understood. Here, we show that activation of D2-like dopamine receptors on DR 5-HT neurons elicits a membrane depolarization and an inward current associated with an increase in membrane conductance. The DA-induced inward current (I(DA)) exhibits a linear I-V relationship and reverses polarity at around -15 mV, suggesting the involvement of a mixed cationic conductance. Consistent with this notion, lowering the extracellular concentration of sodium reduces the amplitude of I(DA) and induces a negative shift of its reversal potential to approximately -45 mV. This current is abolished by inhibiting G-protein function with GDPbetaS. Examination of the downstream signaling mechanisms reveals that activation of the nonselective cation current requires the stimulation of phospholipase C but not an increase in intracellular calcium. Thus, pharmacological inhibition of phospholipase C reduces the amplitude of I(DA). In contrast, buffering intracellular calcium has no effect on the amplitude of I(DA). Bath application of transient receptor potential (TRP) channels blockers, 2-aminoethoxydiphenyl borate and SKF96365 [1-(beta-[3-(4-methoxyphenyl)propoxy]-4-methoxyphenethyl)-1H-imidazole], strongly inhibits I(DA) amplitude, suggesting the involvement of TRP-like conductance. These results reveal previously unsuspected mechanism by which D2-like DA receptors induce membrane depolarization and enhance the excitability of DR 5-HT neurons. PMID:17005915

  11. Cationic Cell-Penetrating Peptide Binds to Planar Lipid Bilayers Containing Negatively Charged Lipids but does not Induce Conductive Pores

    PubMed Central

    Gurnev, Philip A.; Yang, Sung-Tae; Melikov, Kamran C.; Chernomordik, Leonid V.; Bezrukov, Sergey M.

    2013-01-01

    Using a cation-selective gramicidin A channel as a sensor of the membrane surface charge, we studied interactions of oligoarginine peptide R9C, a prototype cationic cell-penetrating peptide (CPP), with planar lipid membranes. We have found that R9C sorption to the membrane depends strongly on its lipid composition from virtually nonexistent for membranes made of uncharged lipids to very pronounced for membranes containing negatively charged lipids, with charge overcompensation at R9C concentrations exceeding 1 μM. The sorption was reversible as it was removed by addition of polyanionic dextran sulfate to the membrane bathing solution. No membrane poration activity of R9C (as would be manifested by increased bilayer conductance) was detected in the charged or neutral membranes, including those with asymmetric negative/neutral and negative/positive lipid leaflets. We conclude that interaction of R9C with planar lipid bilayers does not involve pore formation in all studied lipid combinations up to 20 μM peptide concentration. However, R9C induces leakage of negatively charged but not neutral liposomes in a process that involves lipid mixing between liposomes. Our findings suggest that direct traversing of CPPs through the uncharged outer leaflet of the plasma membrane bilayer is unlikely and that permeabilization necessarily involves both anionic lipids and CPP-dependent fusion between opposing membranes. PMID:23663836

  12. Effect of the alkaline cation size on the conductivity in gel polymer electrolytes and their influence on photo electrochemical solar cells.

    PubMed

    Bandara, T M W J; Fernando, H D N S; Furlani, M; Albinsson, I; Dissanayake, M A K L; Ratnasekera, J L; Mellander, B-E

    2016-04-20

    The nature and concentration of cationic species in the electrolyte exert a profound influence on the efficiency of nanocrystalline dye-sensitized solar cells (DSSCs). A series of DSSCs based on gel electrolytes containing five alkali iodide salts (LiI, NaI, KI, RbI and CsI) and polyacrylonitrile with plasticizers were fabricated and studied, in order to investigate the dependence of solar cell performance on the cation size. The ionic conductivity of electrolytes with relatively large cations, K(+), Rb(+) and Cs(+), was higher and essentially constant, while for the electrolytes containing the two smaller cations, Na(+) and Li(+), the conductivity values were lower. The temperature dependence of conductivity in this series appears to follow the Vogel-Tamman-Fulcher equation. The sample containing the smallest cation shows the lowest conductivity and the highest activation energy of ∼36.5 meV, while K(+), Rb(+) and Cs(+) containing samples show an activation energy of ∼30.5 meV. DSSCs based on the gel electrolyte and a TiO2 double layer with the N719 dye exhibited an enhancement in the open circuit voltage with increasing cation size. This can be attributed to the decrease in the recombination rate of electrons and to the conduction band shift resulting from cation adsorption by TiO2. The maximum efficiency value, 3.48%, was obtained for the CsI containing cell. The efficiencies shown in this study are lower compared to values reported in the literature, and this can be attributed to the use of a single salt and the absence of other additives, since the focus of the present study was to analyze the cation effect. The highest short circuit current density of 9.43 mA cm(-2) was shown by the RbI containing cell. The enhancement of the solar cell performance with increasing size of the cation is discussed in terms of the effect of the cations on the TiO2 anode and ion transport in the electrolyte. In liquid electrolyte based DSSCs, the short circuit current density

  13. Scanning Ion Conductance Microscopic Study for Cellular Uptake of Cationic Conjugated Polymer Nanoparticles.

    PubMed

    Shan, Yuping; Panday, Namuna; Myoung, Yong; Twomey, Megan; Wang, Xuewen; Li, Wenzhi; Celik, Emrah; Moy, Vincent; Wang, Hongda; Moon, Joong Ho; He, Jin

    2016-04-01

    Positively charged conjugated polymer nanoparticles (CPNs) are emerging biomaterials exhibiting high levels of cellular entry. High rate of cellular entry efficiency is believed that the amphiphilic CPNs interact efficiently with the negatively charged hydrophobic cellular membranes. For the first time, the cell surface morphological changes of human cervical cancer cells treated with CPNs using a scanning probe microscopy technique, scanning ion conductance microscopy (SICM) are imaged. After 1 h of CPN incubation, distinct changes are observed in cell surface morphology such as interconnected protrusions and pits with sub-micrometer sizes, which are not observed from cells treated with positively charged polyethyleneimine (PEI) under the same treatment conditions. The change on cell surface morphology is quantified by surface roughness ratio, which is increased as CPN concentration increases, while the ratio first increases and then decreases as the incubation time increases. These results suggest that cells respond actively toward CPN with both positive charges on the side chain and the hydrophobicity from rigid aromatic backbone, which leads to subsequent endocytosis. In conclusion, it is demonstrated that SICM is a suitable imaging technique to reveal the dynamic alternations on the cell surface morphology at the early stage of nanoparticles endocytosis with high resolution. PMID:26757346

  14. The cation selectivity and voltage dependence of the light-activated potassium conductance in scallop distal photoreceptor.

    PubMed Central

    Cornwall, M C; Gorman, A L

    1983-01-01

    Light-dependent voltage and current responses were measured from the distal hyperpolarizing photoreceptors of the scallop (Pecten irradians) retina. In normal external solution, the hyperpolarizing receptor potential was caused by a light-dependent K+ outward current. The magnitude of the hyperpolarizing receptor potential and the light-dependent outward current, measured at the resting potential, was graded with light intensity. In normal external solution, during prolonged illumination the light-dependent K+ outward current was characterized by an early peak and a subsequent plateau. Current responses to brief light flashes were reduced progressively during background illumination. In the absence of external Na+ ions, the reversal potential for the receptor potential changed 58 mV per 10-fold change in the extracellular K+ concentration. The estimated internal K+ concentration was 385 mM. The hyperpolarizing receptor potential produced by prolonged bright illumination consists of an early peak which decays to a plateau. This decay was determined by a decrease in the light-dependent K+ conductance during maintained illumination. The light-dependent conductance pathway passed outward currents better than inward K+ currents. The light-dependent K+ conductance was estimated to increase e-fold per 23-34 mV depolarization at the peak and during the plateau of the light response. The light-dependent conductance pathway was highly selective for K+ ions. The selectivity sequence for monovalent cations was T1+, K+ greater than Rb+ greater than NH4 greater than Cs+, Li+, Na+. External caesium and tetraethylammonium blocked inward but not outward K+ currents through the light-dependent K+ conductance pathway. The data suggest that K+ ions move through an aqueous pore which is controlled by light. PMID:6887051

  15. A solid phase extraction-ion chromatography with conductivity detection procedure for determining cationic surfactants in surface water samples.

    PubMed

    Olkowska, Ewa; Polkowska, Żaneta; Namieśnik, Jacek

    2013-11-15

    A new analytical procedure for the simultaneous determination of individual cationic surfactants (alkyl benzyl dimethyl ammonium chlorides) in surface water samples has been developed. We describe this methodology for the first time: it involves the application of solid phase extraction (SPE-for sample preparation) coupled with ion chromatography-conductivity detection (IC-CD-for the final determination). Mean recoveries of analytes between 79% and 93%, and overall method quantification limits in the range from 0.0018 to 0.038 μg/mL for surface water and CRM samples were achieved. The methodology was applied to the determination of individual alkyl benzyl quaternary ammonium compounds in environmental samples (reservoir water) and enables their presence in such types of waters to be confirmed. In addition, it is a simpler, less time-consuming, labour-intensive, avoiding use of toxic chloroform and significantly less expensive methodology than previously described approaches (liquid-liquid extraction coupled with liquid chromatography-mass spectrometry). PMID:24148395

  16. Functional Chimeras of GLIC Obtained by Adding the Intracellular Domain of Anion- and Cation-Conducting Cys-Loop Receptors

    PubMed Central

    Pandhare, Akash; Fiori, Mariana C.; Goyal, Raman; Pauwels, Jonathan E.; Navetta, Andrew F.; Ahrorov, Afzal; Jansen, Michaela

    2015-01-01

    Pentameric ligand-gated ion channels (pLGICs), also called Cys-loop receptors in eukaryotic superfamily members, play diverse roles in neurotransmission and serve as primary targets for many therapeutic drugs. Structural studies of full-length eukaryotic pLGICs have been challenging because of glycosylation, large size, pentameric assembly, and hydrophobicity. X-ray structures of prokaryotic pLGICs, including the Gloeobacter violaceus LGIC (GLIC) and the Erwinia chrysanthemi LGIC (ELIC), and truncated eukaryotic pLGICs have significantly improved and complemented the understanding of structural details previously obtained with acetylcholine-binding protein and Torpedo nicotinic acetylcholine receptors. Prokaryotic pLGICs share their overall structural features with eukaryotic pLGICs for the ligand-binding extracellular and channel-lining transmembrane domains. The large intracellular domain (ICD) is present only in eukaryotic members and is characterized by a low level of sequence conservation and significant variability in length (50–250 amino acids), making the ICD a potential target for the modulation of specific pLGIC subunits. None of the structures includes a complete ICD. Here, we created chimeras by adding the ICD of cation-conducting (nAChR-α7) and anion-conducting (GABAρ1, Glyα1) eukaryotic homopentamer-forming pLGICs to GLIC. GLIC–ICD chimeras assemble into pentamers to form proton-gated channels, as does the parent GLIC. Additionally, the sensitivity of the chimeras toward modulation of functional maturation by chaperone protein RIC-3 is preserved as in those of the parent eukaryotic channels. For a previously described GLIC–5HT3A–ICD chimera, we now provide evidence of its successful large-scale expression and purification to homogeneity. Overall, the chimeras provide valuable tools for functional and structural studies of eukaryotic pLGIC ICDs. PMID:25861708

  17. Probing the structure of the conduction pathway of the sheep cardiac sarcoplasmic reticulum calcium-release channel with permeant and impermeant organic cations

    PubMed Central

    1993-01-01

    The sarcoplasmic reticulum Ca(2+)-release channel plays a central role in cardiac muscle function by providing a ligand-regulated pathway for the release of sequestered Ca2+ to initiate contraction following cell excitation. The efficiency of the channel as a Ca(2+)-release pathway will be influenced by both gating and conductance properties of the system. In the past we have investigated conduction and discrimination of inorganic mono- and divalent cations with the aim of describing the mechanisms governing ion handling in the channel (Tinker, A., A.R. G. Lindsay, and A.J. Williams. 1992. Journal of General Physiology. 100:495-517.). In the present study, we have used permeant and impermeant organic cations to provide additional information on structural features of the conduction pathway. The use of permeant organic cations in biological channels to explore structural motifs underlying selectivity has been an important tool for the electrophysiologist. We have examined the conduction properties of a series of monovalent organic cations of varying size in the purified sheep cardiac sarcoplasmic reticulum Ca(2+)-release channel. Relative permeability, determined from the reversal potential measured under bi- ionic conditions with 210-mM test cation at the cytoplasmic face of the channel and 210 mM K+ at the luminal, was related inversely to the minimum circular cation radius. The reversal potential was concentration-independent. The excluded area hypothesis, with and without a term for solute-wall friction, described the data well and gave a lower estimate for minimum pore radius of 3.3-3.5 A. Blocking studies with the impermeant charged derivative of triethylamine reveal that this narrowing occurs over the first 10-20% of the voltage drop when crossing from the lumen of the SR to the cytoplasm. Single-channel conductances were measured in symmetrical 210 mM salt. Factors other than relative permeability determine conductance as ions with similar relative

  18. Capillary ion electrophoresis-capacitively coupled contactless conductivity detection of inorganic cations in human saliva on a polyvinyl alcohol-coated capillary.

    PubMed

    Mori, Masanobu; Kaseda, Maki; Yamamoto, Tsukasa; Yamada, Sachiko; Itabashi, Hideyuki

    2012-03-01

    Capillary ion electrophoresis-capacitively coupled contactless conductivity detection (CIE-C4D) with a polyvinyl alcohol chemically coated capillary (PVA capillary) was used to analyze inorganic cations (Na(+), K(+), NH(4)(+), Mg(2+), and Ca(2+)) commonly found in human saliva. The PVA capillary, which was made by our laboratory, minimized electro-osmotic flow in the wide pH range of the background electrolyte (BGE), and the PVA layer adsorbed to capillary wall did not affect the conductimetric background level. In this study, we determined an optimized BGE of 30 mM lactic acid/histidine plus 3 mM 18-crown-6 for the CIE-C4D system using the PVA capillary, which could simultaneously improve the separation of Mg(2+) and Ca(2+) from Na(+) and that of K(+) from NH(4)(+). This system obtained highly reproducible separation of cations in human saliva samples within 8 min at 20 kV without deprotonation. The quantifiability of cations in human saliva samples on the CIE-C4D system was demonstrated through identification by ion chromatography with satisfactory results. PMID:22252656

  19. Actinide cation-cation complexes

    SciTech Connect

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

    1994-12-01

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

  20. Changes of conductance and compressibility of bilayer lipid membranes induced by oligonucleotide-cationic polyene antibiotic complexes.

    PubMed

    Hianik, Tibor; Ostatnik, Lukas; Polohova, Vladimira; Bolard, Jacques

    2008-11-01

    The positively charged polyene molecule amphotericin B 3-dimethylaminopropylamide (AMA) is an efficient agent for the delivery of antisense oligodeoxyribonucleotides (ODN) into target cells. In the present study, bilayer lipid membrane (BLM) conductance, elasticity modulus perpendicular to the membrane plane, surface potential and electrical capacitance were measured by conductance and electrostriction methods in the presence of AMA, pure or complexed to 20-mer single stranded ODN at different ratios. Pure AMA did not induce changes in conductance of cholesterol-containing BLM, but did induce an increase in elasticity modulus and surface potential. ODN/AMA complexes changed BLM properties depending on the charge ratio. The most pronounced effect on membrane conductance was observed for positively charged ODN/AMA complexes (charge ratio rho-/+=0.1), while for negatively charged complexes these changes were less marked/apparent, correlating to substantially lower binding constants. The effect of ODN/AMA complexes on elasticity modulus and charge potential was biphasic. After an increase in both values, a decrease was observed for higher incubation times and ODN/AMA concentrations. These results are interpreted as indicating that the membrane property changes result from the large AMA aggregates induced by the presence of the negatively charged ODN, which condensate on these aggregates. It is suggested that the decrease of elasticity modulus and surface potential in the presence of increasing incubation time and AMA concentration result from desorption of the complexes in the complex-free compartment of the BLM cell, or appearance of a non-linear conductance of the lipid bilayer. The first alternative would explain the AMA-induced transmembrane transfer of ODN. PMID:17904427

  1. Cationic-vacancy-induced room-temperature ferromagnetism in transparent, conducting anatase Ti1-xTaxO2 (x~0.05) thin films.

    PubMed

    Rusydi, A; Dhar, S; Barman, A Roy; Ariando; Qi, D-C; Motapothula, M; Yi, J B; Santoso, I; Feng, Y P; Yang, K; Dai, Y; Yakovlev, N L; Ding, J; Wee, A T S; Neuber, G; Breese, M B H; Ruebhausen, M; Hilgenkamp, H; Venkatesan, T

    2012-10-28

    We report room-temperature ferromagnetism (FM) in highly conducting, transparent anatase Ti(1-x)Ta(x)O(2) (x∼0.05) thin films grown by pulsed laser deposition on LaAlO(3) substrates. Rutherford backscattering spectrometry (RBS), X-ray diffraction, proton-induced X-ray emission, X-ray absorption spectroscopy (XAS) and time-of-flight secondary-ion mass spectrometry indicated negligible magnetic contaminants in the films. The presence of FM with concomitant large carrier densities was determined by a combination of superconducting quantum interference device magnetometry, electrical transport measurements, soft X-ray magnetic circular dichroism (SXMCD), XAS and optical magnetic circular dichroism, and was supported by first-principles calculations. SXMCD and XAS measurements revealed a 90 per cent contribution to FM from the Ti ions, and a 10 per cent contribution from the O ions. RBS/channelling measurements show complete Ta substitution in the Ti sites, though carrier activation was only 50 per cent at 5 per cent Ta concentration, implying compensation by cationic defects. The role of the Ti vacancy (V(Ti)) and Ti(3+) was studied via XAS and X-ray photoemission spectroscopy, respectively. It was found that, in films with strong FM, the V(Ti) signal was strong while the Ti(3+) signal was absent. We propose (in the absence of any obvious exchange mechanisms) that the localized magnetic moments, V(Ti) sites, are ferromagnetically ordered by itinerant carriers. Cationic-defect-induced magnetism is an alternative route to FM in wide-band-gap semiconducting oxides without any magnetic elements. PMID:22987036

  2. On the mechanisms of cation injection in conducting bridge memories: The case of HfO2 in contact with noble metal anodes (Au, Cu, Ag)

    NASA Astrophysics Data System (ADS)

    Saadi, M.; Gonon, P.; Vallée, C.; Mannequin, C.; Grampeix, H.; Jalaguier, E.; Jomni, F.; Bsiesy, A.

    2016-03-01

    Resistance switching is studied in HfO2 as a function of the anode metal (Au, Cu, and Ag) in view of its application to resistive memories (resistive random access memories, RRAM). Current-voltage (I-V) and current-time (I-t) characteristics are presented. For Au anodes, resistance transition is controlled by oxygen vacancies (oxygen-based resistive random access memory, OxRRAM). For Ag anodes, resistance switching is governed by cation injection (Conducting Bridge random access memory, CBRAM). Cu anodes lead to an intermediate case. I-t experiments are shown to be a valuable tool to distinguish between OxRRAM and CBRAM behaviors. A model is proposed to explain the high-to-low resistance transition in CBRAMs. The model is based on the theory of low-temperature oxidation of metals (Cabrera-Mott theory). Upon electron injection, oxygen vacancies and oxygen ions are generated in the oxide. Oxygen ions are drifted to the anode, and an interfacial oxide is formed at the HfO2/anode interface. If oxygen ion mobility is low in the interfacial oxide, a negative space charge builds-up at the HfO2/oxide interface. This negative space charge is the source of a strong electric field across the interfacial oxide thickness, which pulls out cations from the anode (CBRAM case). Inversely, if oxygen ions migration through the interfacial oxide is important (or if the anode does not oxidize such as Au), bulk oxygen vacancies govern resistance transition (OxRRAM case).

  3. Analysis of inorganic cations in biological samples by the combination of micro-electrodialysis and capillary electrophoresis with capacitively coupled contactless conductivity detection.

    PubMed

    Doan, Thi Kieu Oanh; Kubáň, Pavel; Kubáň, Petr; Kiplagat, Isaac K; Boček, Petr

    2011-02-01

    Micro-electrodialysis (μED) and CE were combined for rapid pretreatment and subsequent determination of inorganic cations in biological samples. Combination of μED with CE greatly improved the analytical performance of the latter as the adsorption of high molecular weight compounds present in real samples on the inner capillary wall was eliminated. Fifty microliter of 80-fold diluted human body fluids such as plasma, serum and whole blood was used in the donor compartment of the μED system requiring less than 1 μL of the original body fluid per analysis. Inorganic cations that migrated through a cellulose acetate dialysis membrane with molecular weight cut-off value of 500 Da were collected in the acceptor solution and were then analyzed using CE-C⁴D. Baseline separation of inorganic cations was achieved in a BGE solution consisting of 12.5 mM maleic acid, 15 mM L-arginine and 3 mM 18-crown-6 at pH 5.5. Repeatability of the CE-C⁴D method was better than 0.5% and 2.5% for migration times and peak areas, respectively; limits of detection of all inorganic cations in the presence of 2 mM excess of Na(+) were around 1 μM and calibration curves were linear with correlation coefficients better than 0.998. Repeatability of the sample pretreatment procedure was calculated for six independent electrodialysis runs of artificial and real samples and was better than 11.8%. Recovery values between 96.3 and 110% were achieved for optimized electrodialysis conditions of standard solutions and real samples; lifetime of the dialysis membranes for pretreatment of real samples was estimated to 100 runs. PMID:21298671

  4. The atypical cation-conduction and gating properties of ELIC underscore the marked functional versatility of the pentameric ligand-gated ion-channel fold

    PubMed Central

    Gonzalez-Gutierrez, Giovanni

    2015-01-01

    The superfamily of pentameric ligand-gated ion channels (pLGICs) is unique among ionotropic receptors in that the same overall structure has evolved to generate multiple members with different combinations of agonist specificities and permeant-ion charge selectivities. However, aside from these differences, pLGICs have been typically regarded as having several invariant functional properties. These include pore blockade by extracellular quaternary-ammonium cations in the micromolar-to-millimolar concentration range (in the case of the cation-selective members), and a gain-of-function phenotype, which manifests as a slower deactivation time course, as a result of mutations that reduce the hydrophobicity of the transmembrane pore lining. Here, we tested this notion on three distantly related cation-selective members of the pLGIC superfamily: the mouse muscle nicotinic acetylcholine receptor (nAChR), and the bacterial GLIC and ELIC channels. Remarkably, we found that, whereas low millimolar concentrations of TMA+ and TEA+ block the nAChR and GLIC, neither of these two quaternary-ammonium cations blocks ELIC at such concentrations; instead, both carry measurable inward currents when present as the only cations on the extracellular side. Also, we found that, whereas lidocaine binding speeds up the current-decay time courses of the nAChR and GLIC in the presence of saturating concentrations of agonists, the binding of lidocaine to ELIC slows this time course down. Furthermore, whereas mutations that reduce the hydrophobicity of the side chains at position 9′ of the M2 α-helices greatly slowed the deactivation time course of the nAChR and GLIC, these mutations had little effect—or even sped up deactivation—when engineered in ELIC. Our data indicate that caution should be exercised when generalizing results obtained with ELIC to the rest of the pLGICs, but more intriguingly, they hint at the possibility that ELIC is a representative of a novel branch of the

  5. Effect of Structure on Transport Properties (Viscosity, Ionic Conductivity, and Self-Diffusion Coefficient) of Aprotic Heterocyclic Anion (AHA) Room Temperature Ionic Liquids. 2. Variation of Alkyl Chain Length in the Phosphonium Cation.

    PubMed

    Sun, Liyuan; Morales-Collazo, Oscar; Xia, Han; Brennecke, Joan F

    2016-06-30

    A series of room-temperature ionic liquids (ILs) composed of triethyl(alkyl)phosphonium cations paired with three different aprotic heterocyclic anions (AHAs) (alkyl = butyl ([P2224](+)) and octyl ([P2228](+))) were prepared to investigate the effect of cationic alkyl chain length on transport properties. The transport properties and density of these ILs were measured from 283.15 to 343.15 K at ambient pressure. The dependence of the transport properties (viscosity, ionic conductivity, diffusivity, and molar conductivity) on temperature can be described by the Vogel-Fulcher-Tamman (VFT) equation. The ratio of the molar conductivity obtained from the molar concentration and ionic conductivity measurements to that calculated from self-diffusion coefficients (measured by pulsed gradient spin-echo nuclear magnetic resonance spectroscopy) using the Nernst-Einstein equation was used to quantify the ionicity of these ILs. The molar conductivity ratio decreases with increasing number of carbon atoms in the alkyl chain, indicating that the reduced Coulombic interactions resulting from lower density are more than balanced by the increased van der Waals interactions between the alkyl chains. The results of this study may provide insight into the design of ILs with enhanced dynamics that may be suitable as electrolytes in lithium ion batteries and other electrochemical applications. PMID:27243107

  6. Impact of cation-based localized electronic states on the conduction and valence band structure of Al{sub 1−x}In{sub x}N alloys

    SciTech Connect

    Schulz, S.; Caro, M. A.; O'Reilly, E. P.

    2014-04-28

    We demonstrate that cation-related localized states strongly perturb the band structure of Al{sub 1−x}In{sub x}N leading to a strong band gap bowing at low In content. Our first-principles calculations show that In-related localized states are formed both in the conduction and the valence band in Al{sub 1−x}In{sub x}N for low In composition, x, and that these localized states dominate the evolution of the band structure with increasing x. Therefore, the commonly used assumption of a single composition-independent bowing parameter breaks down when describing the evolution both of the conduction and of the valence band edge in Al{sub 1−x}In{sub x}N.

  7. A New Conducting Molecular Solid Based on the Magnetic [Ni(dmf) 6] 2+ Cation and on [Ni(dsit) 2] 22- (dsit=1,3-dithiole-2-thione-4,5-diselenolate) Showing an Unprecedented Anion Packing

    NASA Astrophysics Data System (ADS)

    Curreli, S.; Deplano, P.; Mercuri, M. L.; Pilia, L.; Serpe, A.; Bigoli, F.; Pellinghelli, M. A.; Coronado, E.; Gómez-Garcıa, C. J.; Canadell, E.

    2002-11-01

    The synthesis, X-ray structure, magnetic and transport properties of the compound Ni(dmf) 6[Ni(dsit) 2] 2 (dmf=dimethylformamide, dsit=1,3-dithiole-2-thione-4,5-diselenolate) are described. This compound crystallizes in the monoclinic space group P2 1/c, with a=18.709(6), b=22.975(5), c=20.418(5) Å, β=99.31(2)° and Z=6; its structure consists of [Ni(dsit) 2] 22- dimers and isolated [Ni(dmf) 6] 2+ cations both centrosymmetric and non-centrosymmetric. The dimers are packed forming chains along the [101] direction with short Se·Se interdimer contacts. Additional interchains S·S contacts render this structure a three-dimensional character, never observed so far in other [Ni(dsit) 2] - salts. This compound exhibits semiconducting behavior with a room temperature conductivity (1 S cm -1) much higher than those reported for other salts of the [Ni(dsit) 2] - anion. Tight-binding band structure calculations were used to analyze the origin of the semiconducting properties of this salt. The magnetic susceptibility shows Curie behavior with C=1.25 emu K mol -1, typical of isolated Ni(II) ions as expected for the octahedrally coordinated [Ni(dmf) 6] 2+ cations.

  8. Cation Ordering in Layered Nickelates

    NASA Astrophysics Data System (ADS)

    Nelson-Cheeseman, Brittany; Zhou, Hua; Cammarata, Antonio; Hoffman, Jason; Balachandran, Prasanna; Rondinelli, James; Bhattacharya, Anand

    2013-03-01

    The single layer Ruddlesden-Popper nickelates present a model system to understand how the effects of digital dopant cation ordering may affect the properties of 2-dimensional conducting sheets. We investigate the effects of aliovalent A-site cation order on LaSrNiO4 films. Using molecular beam epitaxy, we interleave full layers of SrO and LaO in a series of chemically equivalent films, varying the pattern of SrO and LaO layers relative to the NiO2 layers. Through synchrotron surface x-ray diffraction and Coherant Bragg Rod Analysis (COBRA), we directly investigate the A-site cation order and the resulting atomic displacements for each ordering pattern. We correlate these results with theoretical calculations and transport measurements of the layered nickelate films.

  9. Cation Off-Stoichiometry Leads to High p-Type Conductivity and Enhanced Transparency in Co2ZnO4 and Co2NiO4 Thin Films

    SciTech Connect

    Zakutayev, A.; Paudel, T. R.; Ndione, P. F.; Perkins, J. D.; Lany, S.; Zunger, A.; Ginley, D. S.

    2012-02-15

    We explore the effects of cation off-stoichiometry on structural, electrical, optical, and electronic properties of Co{sub 2}ZnO{sub 4} normal spinel and Co{sub 2}NiO{sub 4} inverse spinel using theoretic and experimental (combinatorial and conventional) techniques, both at thermodynamic equilibrium and in the metastable regime. Theory predicts that nonequilibrium substitution of divalent Zn on nominally trivalent octahedral sites increases net hole density in Co{sub 2}ZnO{sub 4}. Experiment confirms high conductivity and high work function in Co{sub 2}NiO{sub 4} and Zn-rich Co{sub 2}ZnO{sub 4} thin films grown by nonequilibrium physical vapor deposition techniques. High p-type conductivities of Co{sub 2}ZnO{sub 4} (up to 5 S/cm) and Co{sub 2}NiO{sub 4} (up to 204 S/cm) are found over a broad compositional range, they are only weakly sensitive to oxygen partial pressure and quite tolerant to a wide range of processing temperatures. In addition, off-stoichiometry caused by nonequilibrium growth decreases the optical absorption of Co{sub 2}ZnO{sub 4} and Co{sub 2}NiO{sub 4} thin films, although the 500-nm thin films still have rather limited transparency. All these properties as well as high work functions make Co{sub 2}ZnO{sub 4} and Co{sub 2}NiO{sub 4} thin films attractive for technological applications, such as hole transport layers in organic photovoltaic devices or p-type buffer layers in inorganic solar cells.

  10. The cubyl cation rearrangements.

    PubMed

    Jalife, Said; Mondal, Sukanta; Cabellos, Jose Luis; Martinez-Guajardo, Gerardo; Fernandez-Herrera, Maria A; Merino, Gabriel

    2016-02-25

    Born-Oppenheimer molecular dynamics simulations and high-level ab initio computations predict that the cage-opening rearrangement of the cubyl cation to the 7H(+)-pentalenyl cation is feasible in the gas phase. The rate-determining step is the formation of the cuneyl cation with an activation barrier of 25.3 kcal mol(-1) at the CCSD(T)/def2-TZVP//MP2/def2-TZVP level. Thus, the cubyl cation is kinetically stable enough to be formed and trapped at moderate temperatures, but it may be rearranged at higher temperatures. PMID:26880646

  11. Cation locations and dislocations in zeolites

    NASA Astrophysics Data System (ADS)

    Smith, Luis James

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

  12. ADSORPTION OF ORGANIC CATIONS TO SOILS AND SUBSURFACE MATERIALS

    EPA Science Inventory

    A study of the fundamentals of adsorption of amphiphilic organic cations on natural and pristine surfaces was conducted to elucidate (i) the factors that influence the extent of adsorption and (ii) indirect effects of adsorption of organic cations: the competitive adsorption of o...

  13. Cationically polymerizable monomers derived from renewable sources

    SciTech Connect

    Crivello, J.V.

    1991-10-01

    The objective of this project is to make use of products obtained from renewable plant sources as monomers for the direct production of polymers which can be used for a wide range of plastic applications. In this report is described progress in the synthesis and polymerization of cationically polymerizable monomers and oligomers derived from botanical oils, terpenes, natural rubber, and lignin. Nine different botanical oils were obtained from various sources, characterized and then epoxidized. Their photopolymerization was carried out using cationic photoinitiators and the mechanical properties of the resulting polymers characterized. Preliminary biodegradation studies are being conducted on the photopolymerized films from several of these oils. Limonene was cationically polymerized to give dimers and the dimers epoxidized to yield highly reactive monomers suitable for coatings, inks and adhesives. The direct phase transfer epoxidation of squalene and natural rubber was carried out. The modified rubbers undergo facile photocrosslinking in the presence of onium salts to give crosslinked elastomers. 12 refs., 3 figs., 10 tabs.

  14. 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

  15. Cation-coupled bicarbonate transporters.

    PubMed

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

    2014-10-01

    Cation-coupled HCO3(-) transport was initially identified in the mid-1970s when pioneering studies showed that acid extrusion from cells is stimulated by CO2/HCO3(-) and associated with Na(+) and Cl(-) movement. The first Na(+)-coupled bicarbonate transporter (NCBT) was expression-cloned in the late 1990s. There are currently five mammalian NCBTs in the SLC4-family: the electrogenic Na,HCO3-cotransporters NBCe1 and NBCe2 (SLC4A4 and SLC4A5 gene products); the electroneutral Na,HCO3-cotransporter NBCn1 (SLC4A7 gene product); the Na(+)-driven Cl,HCO3-exchanger NDCBE (SLC4A8 gene product); and NBCn2/NCBE (SLC4A10 gene product), which has been characterized as an electroneutral Na,HCO3-cotransporter or a Na(+)-driven Cl,HCO3-exchanger. Despite the similarity in amino acid sequence and predicted structure among the NCBTs of the SLC4-family, they exhibit distinct differences in ion dependency, transport function, pharmacological properties, and interactions with other proteins. In epithelia, NCBTs are involved in transcellular movement of acid-base equivalents and intracellular pH control. In nonepithelial tissues, NCBTs contribute to intracellular pH regulation; and hence, they are crucial for diverse tissue functions including neuronal discharge, sensory neuron development, performance of the heart, and vascular tone regulation. The function and expression levels of the NCBTs are generally sensitive to intracellular and systemic pH. Animal models have revealed pathophysiological roles of the transporters in disease states including metabolic acidosis, hypertension, visual defects, and epileptic seizures. Studies are being conducted to understand the physiological consequences of genetic polymorphisms in the SLC4-members, which are associated with cancer, hypertension, and drug addiction. Here, we describe the current knowledge regarding the function, structure, and regulation of the mammalian cation-coupled HCO3(-) transporters of the SLC4-family. PMID:25428855

  16. Cation-Coupled Bicarbonate Transporters

    PubMed Central

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

    2016-01-01

    Cation-coupled HCO3− transport was initially identified in the mid-1970s when pioneering studies showed that acid extrusion from cells is stimulated by CO2/HCO3− and associated with Na+ and Cl− movement. The first Na+-coupled bicarbonate transporter (NCBT) was expression-cloned in the late 1990s. There are currently five mammalian NCBTs in the SLC4-family: the electrogenic Na,HCO3-cotransporters NBCe1 and NBCe2 (SLC4A4 and SLC4A5 gene products); the electroneutral Na,HCO3-cotransporter NBCn1 (SLC4A7 gene product); the Na+-driven Cl,HCO3-exchanger NDCBE (SLC4A8 gene product); and NBCn2/NCBE (SLC4A10 gene product), which has been characterized as an electroneutral Na,HCO3-cotransporter or a Na+-driven Cl,HCO3-exchanger. Despite the similarity in amino acid sequence and predicted structure among the NCBTs of the SLC4-family, they exhibit distinct differences in ion dependency, transport function, pharmacological properties, and interactions with other proteins. In epithelia, NCBTs are involved in transcellular movement of acid-base equivalents and intracellular pH control. In nonepithelial tissues, NCBTs contribute to intracellular pH regulation; and hence, they are crucial for diverse tissue functions including neuronal discharge, sensory neuron development, performance of the heart, and vascular tone regulation. The function and expression levels of the NCBTs are generally sensitive to intracellular and systemic pH. Animal models have revealed pathophysiological roles of the transporters in disease states including metabolic acidosis, hypertension, visual defects, and epileptic seizures. Studies are being conducted to understand the physiological consequences of genetic polymorphisms in the SLC4-members, which are associated with cancer, hypertension, and drug addiction. Here, we describe the current knowledge regarding the function, structure, and regulation of the mammalian cation-coupled HCO3− transporters of the SLC4-family. PMID:25428855

  17. MLKL forms cation channels

    PubMed Central

    Xia, Bingqing; Fang, Sui; Chen, Xueqin; Hu, Hong; Chen, Peiyuan; Wang, Huayi; Gao, Zhaobing

    2016-01-01

    The mixed lineage kinase domain-like (MLKL) protein is a key factor in tumor necrosis factor-induced necroptosis. Recent studies on necroptosis execution revealed a commitment role of MLKL in membrane disruption. However, our knowledge of how MLKL functions on membrane remains very limited. Here we demonstrate that MLKL forms cation channels that are permeable preferentially to Mg2+ rather than Ca2+ in the presence of Na+ and K+. Moreover, the N-terminal domain containing six helices (H1-H6) is sufficient to form channels. Using the substituted cysteine accessibility method, we further determine that helix H1, H2, H3, H5 and H6 are transmembrane segments, while H4 is located in the cytoplasm. Finally, MLKL-induced membrane depolarization and cell death exhibit a positive correlation to its channel activity. The Mg2+-preferred permeability and five transmembrane segment topology distinguish MLKL from previously identified Mg2+-permeable channels and thus establish MLKL as a novel class of cation channels. PMID:27033670

  18. NMR studies of cation transport across membranes

    SciTech Connect

    Shochet, N.R.

    1985-01-01

    /sup 23/Na NMR Studies of cation transport across membranes were conducted both on model and biological membranes. Two ionophores, the carrier monensin and the channel-former gramicidin, were chosen to induce cation transport in large unilamellar phosphatidylcholine vesicles. The distinction between the NMR signals arising from the two sides of the membrane was achieved by the addition of an anionic paramagnetic shift reagent to the outer solution. The kinetics of the cation transport across the membrane was observed simultaneously monitoring the changes in the /sup 23/Na NMR signals of both compartments. Two mathematical models were developed for the estimation of the transport parameters of the monensin- and gramicidin-induced cation transport. The models were able to fit the experimental data very well. A new method for the estimation of the volume trapped inside the vesicles was developed. The method uses the relative areas of the intra- and extravesicular NMR signals arising from a suspension of vesicles bathed in the same medium they contain, as a measure for the relative volumes of these compartments. Sodium transport across biological membranes was studied by /sup 23/ NMR, using suspensions of cultured nerve cells. The sodium influx through voltage-gated channels was studied using the channel modifier batrachotoxin in combination with scorpion toxin.

  19. Anion, cation, and zwitterion selectivity of phospholemman channel molecules.

    PubMed Central

    Kowdley, G C; Ackerman, S J; Chen, Z; Szabo, G; Jones, L R; Moorman, J R

    1997-01-01

    Phospholemman (PLM), a 72-amino acid membrane protein with a single transmembrane domain, forms taurine-selective ion channels in lipid bilayers. Because taurine forms zwitterions, a taurine-selective channel might have binding sites for both anions and cations. Here we show that PLM channels indeed allow fluxes of both cations and anions, making instantaneous and voltage-dependent transitions among conformations with drastically different ion selectivity characteristics. This surprising and novel ion channel behavior offers a molecular explanation for selective taurine flux across cell membranes and may explain why molecules in the phospholemman family can induce cation- or anion-selective conductances when expressed in Xenopus oocytes. PMID:8994599

  20. Structurally Distinct Cation Channelrhodopsins from Cryptophyte Algae.

    PubMed

    Govorunova, Elena G; Sineshchekov, Oleg A; Spudich, John L

    2016-06-01

    Microbial rhodopsins are remarkable for the diversity of their functional mechanisms based on the same protein scaffold. A class of rhodopsins from cryptophyte algae show close sequence homology with haloarchaeal rhodopsin proton pumps rather than with previously known channelrhodopsins from chlorophyte (green) algae. In particular, both aspartate residues that occupy the positions of the chromophore Schiff base proton acceptor and donor, a hallmark of rhodopsin proton pumps, are conserved in these cryptophyte proteins. We expressed the corresponding polynucleotides in human embryonic kidney (HEK293) cells and studied electrogenic properties of the encoded proteins with whole-cell patch-clamp recording. Despite their lack of residues characteristic of the chlorophyte cation channels, these proteins are cation-conducting channelrhodopsins that carry out light-gated passive transport of Na(+) and H(+). These findings show that channel function in rhodopsins has evolved via multiple routes. PMID:27233115

  1. Modification of ion transport in lipid bilayer membranes in the presence of 2,4-dichlorophenoxyacetic acid. I. Enhancement of cationic conductance and changes of the kinetics of nonactin-mediated transport of potassium.

    PubMed Central

    Smejtek, P; Paulis-Illangasekare, M

    1979-01-01

    We have found that herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) has the ability to increase the rate of transport of positive ions of several kinds, and to inhibit transport of negatively charged tetraphenylborate ions in lipid bilayer membranes. It has been found that only the neutral form of 2,4-D is transport active, whereas the ionized from of 2,4-D does not modify transport of ions, and does not by itself permeate through lipid membranes. The results suggest that the enhancement of transport of positively charged ions such as tetraphenylarsonium + and nonactin-K+ is dominated by the increase of the ion translocation rate constant. It has been shown that the enhancement of nonactin-mediated transport of K+ by 2,4-D can be accounted for by a simple carrier model. We have observed that a 2,4-D concentration above 3 X 10(-4) M the potassium ion transport in phosphatidylcholine-cholesterol as well as in cholesterol-free glycerolmonooleate membranes is enhanced to such a degree that, depending upon the concentration of potassium ions, it becomes limited by the rate of recombination of K+ with nonactin, and/or by backdiffusion of unloaded nonactin molecules. Furthermore, the effect of 2,4-D is enhanced by ionic strength of aqueous solution. From the changes of kinetic parameters of nonactin-K+ transport, as well as from the changes of membranes conductance due to tetraphenylarsonium + ions, we have estimated the changes of the electrical potential of the membrane interior. We have found that the potential of the interior of the membrane becomes more negative in the presence of 2,4-D, and that its change is proportional to the aqueous concentration of 2,4-D. The effect of 2,4-D on ion transport has been attributed to a layer of 2,4-D molecules absorbed within the interfacial region, and having a dipole moment directed toward the aqueous medium. The results of kinetic studied of nonactin-K+ transport suggest that this layer is located on the hydrocarbon side of the

  2. CATION TRANSPORT AND PARTITIONING DURING A FIELD TEST OF ELECTROOSMOSIS

    EPA Science Inventory

    Field experiments were conducted to evaluate the effects of soil properties, such as the cation exchange capacity and mineral content, on pH, soluble ion concentrations, and electrical conductivity during electroosmosis in a silty clay soil. The soil is composed mainly of quartz ...

  3. Dissecting the cation-cation interaction between two uranyl units.

    PubMed

    Tecmer, Paweł; Hong, Sung W; Boguslawski, Katharina

    2016-07-21

    We present a state-of-the-art computational study of the uranyl(vi) and uranyl(v) cation-cation interactions (dications) in aqueous solution. Reliable electronic structures of two interacting uranyl(vi) and uranyl(v) subunits as well as those of the uranyl(vi) and uranyl(v) clusters are presented for the first time. Our theoretical study elucidates the impact of cation-cation interactions on changes in the molecular structure as well as changes in vibrational and UV-Vis spectra of the bare uranyl(vi) and uranyl(v) moieties for different total spin-states and total charges of the dications. PMID:27335229

  4. 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

  5. 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

  6. Cationic lipid-mediated nucleic acid delivery: beyond being cationic.

    PubMed

    Rao, N Madhusudhana

    2010-03-01

    Realization of the potential of nucleic acids as drugs is intricately linked to their in vivo delivery. Cationic lipids demonstrated tremendous potential as safe, efficient and scalable in vitro carriers of nucleic acids. For in vivo delivery of nucleic acids, the extant two component liposomal preparations consisting of cationic lipids and nucleic acids have been largely found to be insufficient. Being a soft matter, liposomes readily respond to many physiological variables leading to complex component and morphological changes, thus confounding the efforts in a priori identification of a "competent" formulation. In the recent past many chemical moieties that provide advantage in facing the challenges of barriers in vivo, were incorporated into cationic lipids to improve the transfection efficiency. The cationic lipids, essential for DNA condensation and protection, definitely require additional components to be efficient in vivo. In addition, formulations of cationic lipid carriers with non-lipidic components, mainly peptides, have demonstrated success in in vivo transfection. The present review describes some recent successes of in vivo nucleic acid delivery by cationic lipids. PMID:20060819

  7. Novel penetrating cations for targeting mitochondria.

    PubMed

    Chernyak, Boris V; Antonenko, Yuri N; Domnina, Lidia V; Ivanova, Olga Yu; Lyamzaev, Konstantin G; Pustovidko, Antonina V; Rokitskaya, Tatiana I; Severina, Inna I; Simonyan, Ruben A; Trendeleva, Tatiana A; Zvyagilskaya, Renata A

    2013-01-01

    Novel penetrating cations were used for the design of mitochondria-targeted compounds and tested in model lipid membranes, in isolated mitochondria and in living human cells in culture. Rhodamine-19, berberine and palmatine were conjugated by aliphatic linkers with plastoquinone possessing antioxidant activity. These conjugates (SkQR1,SkQBerb, SkQPalm) and their analogs lacking plastoquinol moiety (C12R1,C10Berb and C10Palm) penetrated bilayer phospholipid membrane in their cationic forms and accumulated in isolated mitochondria or in mitochondria of living cells due to membrane potential negative inside. Reduced forms of SkQR1, SkQBerb and SkQPalm inhibited lipid peroxidation in isolated mitochondria at nanomolar concentrations. In human fibroblasts SkQR1, SkQBerb and SkQPalm prevented fragmentation of mitochondria and apoptosis induced by hydrogen peroxide. SkQR1 was effective at subnanomolar concentrations while SkQberb, SkQPalm and SkQ1 (prototypic conjugate of plastoquinone with dodecyltriphenylphosphonium) were effective at 10-times higher concentrations. The aliphatic conjugates of berberine and palmatine (as well as the conjugates of triphenylphosphonium) induced proton transport mediated by free fatty acids (FA) both in the model and mitochondrial membrane. In mitochondria this process was facilitated by the adenine nucleotide carrier. In contrast to the other cationic conjugates, SkQR1 and C12R1 induced FA-independent proton conductivity due to protonation/deprotonation of the rhodamine residue. This property in combination with the antioxidant activity probably makes rhodamine conjugates highly effective in protection against oxidative stress. The novel cationic conjugates described here are promising candidates for drugs against various pathologies and aging as mitochondria-targeted antioxidants and selective mild uncouplers. PMID:23092317

  8. Cation Diffusion in Xenotime

    NASA Astrophysics Data System (ADS)

    Cherniak, D. J.

    2004-05-01

    Xenotime is an important mineral in metamorphic paragenesis, and useful in isotopic dating, garnet-xenotime thermometry, and monazite-xenotime thermometry, so diffusion data for xenotime of cations of geochronological and geochemical importance are of some interest. We report here on diffusion of the rare earth elements Sm, Dy and Yb in synthetic xenotime under dry conditions. The synthetic xenotime was grown via a Na2}CO{3}-MoO_{3 flux method. The source of diffusant for the experiments were REE phosphate powders, with experiments run with sources containing a single REE. Experiments were performed by placing source and xenotime in Pt capsules, and annealing capsules in 1 atm furnaces for times ranging from thirty minutes to a month, at temperatures from 1000 to 1400C. The REE distributions in the xenotime were profiled by Rutherford Backscattering Spectrometry (RBS). The following Arrhenius relations are obtained for diffusion in xenotime, normal to (101): DSm = 1.7x10-4 exp(-442 kJ mol-1/RT) m2}sec{-1 DDy = 3.5x10-7 exp(-365 kJ mol-1/RT) m2}sec{-1 DYb = 7.4x10-7 exp(-371 kJ mol-1/RT) m2}sec{-1. Diffusivities of these REE do not differ greatly in xenotime, in contrast to the findings noted for the REE in zircon (Cherniak et al., 1997), where the LREE diffuse more slowly, and with higher activation energies for diffusion, than the heavier rare earths. In zircon, these differences among diffusion of the rare earths are attributed to the relatively large size of the REE with respect to Zr, for which they substitute in the zircon lattice. With the systematic increase in ionic radius from the heavy to lighter REE, this size mismatch becomes more pronounced and diffusivities of the LREE are as consequence slower. Although xenotime is isostructural with zircon, the REE are more closely matched in size to Y, so in xenotime this effect appears much smaller and the REE diffuse at similar rates. In addition, the process of diffusion in xenotime likely involves simple REE+3

  9. Versatile cation transport in imidazolium based polymerized ionic liquids

    NASA Astrophysics Data System (ADS)

    Evans, Christopher; Segalman, Rachel

    Polymerized ionic liquids (PIL) with tethered imidazolium groups are able to conduct a diverse array of cations relevant for energy applications. The well-known complexation of imidazolium with transition metals is exploited to bind ions such as H +, Li+, Cu2+, and Ni2+ by doping the neutral PIL with the appropriate Cation-TFSI- salt. Conductivities were first determined via AC impedance indicating that H+ salts lead to the highest conductivity (due to low ion mass and potential Grotthus mechanism) followed by Cu2+, Li+, Ag+, and Ni2+. The equilibrium constant for imidazolium complexation is larger for Cu2+ relative to Li-, Ag-, and Ni-imidazolium complexes leading to greater salt dissociation and higher conductivities. For LiTFSI and CuTFSI2 salts, metallic lithium or copper electrodes were employed in battery cells to pass a steady DC current and confirm that the cations are in fact carrying current. Interestingly, the divalent Cu2+ also ionically crosslinks the polymer leading to a plateau in the viscosity. Thus, divalent ions provide an unique route to high conductivity, high modulus polymeric electrolytes. Future studies involving ZnTFSI2 and MgTFSI2 for battery applications are proposed to examine how versatile the PIL platform is for cation transport.

  10. Hydroxide Degradation Pathways for Substituted Trimethylammonium Cations: A DFT Study

    SciTech Connect

    Long, H.; Kim, K.; Pivovar, B. S.

    2012-05-03

    Substituted trimethylammonium cations serve as small molecule analogues for tetherable cations in anion exchange membranes. In turn, these membranes serve as the basis for alkaline membrane fuel cells by allowing facile conduction of hydroxide. As these cations are susceptible to hydroxide attack, they degrade over time and greatly limit the lifetime of the fuel cell. In this research, we performed density functional theory calculations to investigate the degradation pathways of substituted trimethylammonium cations to probe the relative durability of cation tethering strategies in alkyl and aromatic tethers. Our results show that significant changes in calculated energy barriers occur when substitution groups change. Specifically, we have found that, when available, the Hofmann elimination pathway is the most vulnerable pathway for degradation; however, this barrier is also found to depend on the carbon chain length and number of hydrogens susceptible to Hofmann elimination. S{sub N}2 barriers were also investigated for both methyl groups and substitution groups. The reported findings give important insight into potential tethering strategies for trimethylammonium cations in anion exchange membranes.

  11. A cation counterflux supports lysosomal acidification

    PubMed Central

    Steinberg, Benjamin E.; Huynh, Kassidy K.; Brodovitch, Alexandre; Jabs, Sabrina; Stauber, Tobias; Jentsch, Thomas J.

    2010-01-01

    The profound luminal acidification essential for the degradative function of lysosomes requires a counter-ion flux to dissipate an opposing voltage that would prohibit proton accumulation. It has generally been assumed that a parallel anion influx is the main or only counter-ion transport that enables acidification. Indeed, defective anion conductance has been suggested as the mechanism underlying attenuated lysosome acidification in cells deficient in CFTR or ClC-7. To assess the individual contribution of counter-ions to acidification, we devised means of reversibly and separately permeabilizing the plasma and lysosomal membranes to dialyze the cytosol and lysosome lumen in intact cells, while ratiometrically monitoring lysosomal pH. Replacement of cytosolic Cl− with impermeant anions did not significantly alter proton pumping, while the presence of permeant cations in the lysosomal lumen supported acidification. Accordingly, the lysosomes were found to acidify to the same pH in both CFTR- and ClC-7–deficient cells. We conclude that cations, in addition to chloride, can support lysosomal acidification and defects in lysosomal anion conductance cannot explain the impaired microbicidal capacity of CF phagocytes. PMID:20566682

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

    SciTech Connect

    Shi, Zhenqing; Balogh-Brunstad, Zsuzsanna; Grant, Michael R.; Harsh, James B.; Gill, Richard; Thomashow, Linda; Dohnalkova, Alice; Stacks, Daryl; Letourneau, Melissa; Keller, Chester K.

    2014-01-10

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

  13. Permeation of Water through Cation Exchange Membranes

    PubMed Central

    Lakshminarayanaiah, N.

    1967-01-01

    Water permeabilities as well as other membrane parameters, such as exchange capacity, water content, and specific conductance, have been measured for two cation exchange membranes in the H form. The conductance of membrane with low water content was less than that of the membrane with high water content. These data have been discussed in the light of an existing theory and found inadequate to explain the results in a quantitative way. Water permeability of the membranes subject to mechanical pressure was found to be higher than their isotopic water permeability, according to expectation. These data have been examined from the standpoint of thermodynamic and kinetic theories of water flow in membranes and used to estimate the average size of membrane pores. PMID:6048874

  14. Cation-cation interactions and cation exchange in a series of isostructural framework uranyl tungstates

    NASA Astrophysics Data System (ADS)

    Balboni, Enrica; Burns, Peter C.

    2014-05-01

    The isotypical compounds (UO2)3(WO6)(H2O)5 (1), Ag(UO2)3(WO6)(OH)(H2O)3 (2), K(UO2)3(WO6)OH(H2O)4 (3), Rb(UO2)3(WO6)(OH)(H2O)3.5 (4), and Cs(UO2)3(WO6)OH(H2O)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 a 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 (UO2)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 WO6 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.

  15. Synergistic effects of intrinsic cation disorder and electron-deficient substitution on ion and electron conductivity in La1-xSrxCo0.5Mn0.5O3-δ (x = 0, 0.5, and 0.75).

    PubMed

    Meng, Junling; Yuan, Na; Liu, Xiaojuan; Yao, Chuangang; Liang, Qingshuang; Zhou, Defeng; Meng, Fanzhi; Meng, Jian

    2015-03-16

    The effects of intrinsic cation disorder and electron-deficient substitution for La1-xSrxCo0.5Mn0.5O3-δ (LSCM, x = 0, 0.5, and 0.75) on oxygen vacancy formation, and their influence on the electrochemical properties, were revealed through a combination of computer simulation and experimental study. First-principles calculations were first performed and found that the tendency of the oxygen vacancy formation energy was Mn(3+)-O*-Mn(4+) < Co(2+)-O*-Co(3+) < Co(2+)-O*-Mn(4+), meaning that antisite defects not only facilitate the formation of oxygen vacancy but introduce the mixed-valent transition-metal pairs for high electrical conductivity. Detailed partial density of states (PDOS) analysis for Mn on Co sites (MnCo) and Co on Mn sites (CoMn) indicate that Co(2+) is prone to being Co(3+) while Mn(4+) is prone to being Mn(3+) when they are on antisites, respectively. Also it was found that the holes introduced by Sr tend to enter the Co sublattice for x = 0.5 and then the O sublattice when x = 0.75, which further promotes oxygen vacancy formation, and these results are confirmed by both the calculated PDOS results and charge-density difference. On the basis of microscopic predictions, we intentionally synthesized a series of pure LSCM compounds and carried out comprehensive characterization. The crystal structures and their stability were characterized via powder X-ray Rietveld refinements and in situ high-temperature X-ray diffraction. X-ray photoelectron spectroscopy testified to the mixed oxidation states of Co(2+)/Co(3+) and Mn(3+)/Mn(4+). The thermal expansion coefficients were found to match the Ce0.8Sm0.2O2-δ electrolyte well. The electrical conductivities were about 41.4, 140.5, and 204.2 S cm(-1) at doping levels of x = 0, 0.5, and 0.75, and the corresponding impedances were 0.041, 0.027, and 0.022 Ω cm(2) at 850 °C, respectively. All of the measured results testify that Sr-doped LaCo0.5Mn0.5O3 compounds are promising cathode materials for intermediate

  16. Halogenated silanes, radicals, and cations

    NASA Astrophysics Data System (ADS)

    Wang, Liming; He, Yi-Liang

    2008-09-01

    Quantum chemistry study has been carried out on the structure and energetics of halogenated silanes, radicals, and cations (SiHxXy0,+1, X = F, Cl, Br; x + y = 1-4). The geometries are optimized at B3LYP/6-31+G(2df,p) level. The adiabatic ionization energiess (IEas), relative energetics of cations, proton affinities (PAs) of silanes, and the enthalpies of formation are predicted using G3(CC) model chemistry. Non-classical ion complex structures are found for hydrogenated cations and transition states connecting classical and non-classical structures are also located. The most stable cations for silylene and silyl radicals have their classical divalent and trivalent structures, and those for silanes have non-classical structures except for SiH3Br+ and SiH2Br2+. The non-classical structures for halosilane cations imply difficulty in experimentally measurement of the adiabatic ionization energies using photoionization or photoelectron studies. For SiH3X, SiH2X2, and SiHX3, the G3(CC) adiabatic IEas to classical ionic structures closest to their neutrals agree better with the photoelectron spectroscopic measurements. The transition states between classical and non-classical structures also hamper the photoionization determination of the appearance energies for silylene cations from silanes. The G3(CC) results for SiHx0,+1 agree excellently with the photoionization mass spectrometric study, and the results for fluorinated and chlorinated species also agree with the previous theoretical predictions at correlation levels from BAC-MP4 to CCSD(T)/CBS. The predicted enthalpy differences between SiH2Cl+, SiHCl2+, and SiCl3+ are also in accordance with previous kinetics study. The G3(CC) results show large discrepancies to the collision-induced charge transfer and/or dissociation reactions involving SiFx+ and SiClx+ ions, for which the G3(CC) enthalpies of formation are also significantly differed from the previous theoretical predictions, especially on SiFx+ (x = 2-4). The G3

  17. Conductive hydrogel containing 3-ionene

    NASA Technical Reports Server (NTRS)

    Rembaum, Alan (Inventor); Yen, Shiao-Ping Siao (Inventor)

    1977-01-01

    Cationic polyelectrolytes formed by the polymerization in absence of oxygen of a monomer of the general formula: dispersed ##STR1## where x is 3 or more than 6 and Z is I, Br or Cl to form high charge density linear polymers are dispered in a water-soluble polymer such as polyvinyl alcohol to form a conductive hydrogel.

  18. Electrical Conductivity in Transition Metals

    ERIC Educational Resources Information Center

    Talbot, Christopher; Vickneson, Kishanda

    2013-01-01

    The aim of this "Science Note" is to describe how to test the electron-sea model to determine whether it accurately predicts relative electrical conductivity for first-row transition metals. In the electron-sea model, a metal crystal is viewed as a three-dimensional array of metal cations immersed in a sea of delocalised valence…

  19. 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.

  20. Gaseous protein cations are amphoteric

    SciTech Connect

    Stephenson, J.L. Jr.; McLuckey, S.A.

    1997-02-19

    Singly- and multiply-protonated ubiquitin molecules are found to react with iodide anions, and certain other anions, by attachment of the anion, in competition with proton transfer to the anion. The resulting adduct ions are relatively weakly bound and dissociate upon collisional activation by loss of the neutral acid derived from the anion. Adduct ions that behave similarly can also be formed via ion/molecule reactions involving the neutral acid. The ion/molecule reaction phenomenology, however, stands in contrast with that expected based on the reaction site(s) being charged. Reaction rates increase inversely with charge state and the total number of neutral molecules that add to the protein cations increases inversely with cation charge. These observations are inconsistent with the formation of proton-bound clusters but are fully consistent with the formation of ion pairs or dipole/dipole bonding involving the neutral acid and neutral basic sites in the protein. The ion/ion reactions can be interpreted on the basis of conjugate acid/base chemistry in which the anion, which is a strong gaseous base, reacts with a protonated site, which is a strong gaseous acid. Adduct ions can also be formed via ion/molecule reaction which, on the basis of microscopic reversibility, implies that the neutral acid interacts with neutral basic sites on the protein cation. 26 refs., 10 figs., 1 tab.

  1. Hyperconjugation in diethyl ether cation versus diethyl sulfide cation.

    PubMed

    Morita, Masato; Matsuda, Yoshiyuki; Endo, Tomoya; Mikami, Naohiko; Fujii, Asuka; Takahashi, Kaito

    2015-09-28

    Ionization of a molecule can greatly alter its electronic structure as well as its geometric structure. In this collaborative experimental and theoretical study, we examined variance in hyperconjugation upon ionization of diethyl ether (DEE) and diethyl sulfide (DES). We obtained the experimental gas phase vibrational spectra of DEE, DES, DEE(+), DES(+), DEE(+)-Ar, and DES(+)-Ar in the wavenumber region of 2500 to 3600 cm(-1). For DEE(+) and DEE(+)-Ar, we observed a greatly red shifted CH stretching peak at 2700 cm(-1), while the lowest CH stretching peaks for DEE, DES, DES(+) and DES(+)-Ar were observed around 2850 cm(-1). For DEE(+), we calculated a drastic red shifted CH stretching peak at 2760 cm(-1), but for DEE, DES, and DES(+) the lowest CH stretching peaks were calculated to be at 2860, 2945, and 2908 cm(-1), respectively. In addition, for DEE, the minima (maxima) geometry in the neutral state becomes a maxima (minima) geometry in the cationic state, while similar minima geometries are seen in neutral and cationic states of DES. These experimental and theoretical findings were rationalized through the natural bond orbital analysis by quantifying the hyperconjugation between the σCH orbital and the ionized singly occupied p orbital of the oxygen (sulfur) in DEE(+) (DES(+)). This study showed how orientation with the ionized orbital can greatly affect the neighboring CH bond strength and its polarity, as well as the geometry of the system. Furthermore, this change in the CH bond strength between DEE(+) and DES(+) is quantified from the energies for intramolecular proton transfer in the two cations. PMID:26300267

  2. Cation coordination in oxychloride glasses

    NASA Astrophysics Data System (ADS)

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

    2003-02-01

    Glasses containing mixtures of cations and anions of nominal compositions [Sb2O3]x - [ZnCl2]1-x where x = 0.25, 0.50, 0.75, and 1.00, have been studied by means of neutron diffraction and Raman and Mössbauer spectroscopy. There is preferential bonding within the system with the absence of Sb-Cl bonds. Antimony is found to be threefold coordinated to oxygen, and zinc fourfold coordinated. The main contributing species are of the form [Sb(OSb)2(OZn)] and [Zn(ClZn)2(OSb)2].

  3. Use of laser induced photoacoustic spectroscopy (LIPAS) to determine equilibrium constants of cation-cation complexes

    SciTech Connect

    Hannink, N.J.; Hoffman, D.C.; Silva, R.J.; Russo, R.E.

    1993-12-31

    Laser Induced PhotoAcoustic Spectroscopy (LIPAS) is a relatively new, photothermal technique to examine solutions. Studies in the past have shown it to be more sensitive than conventional absorption spectroscopy, while, yielding the same information thus allowing lower concentrations to be used. This study is using LIPAS to examine solutions to determine the equilibrium constants of cation-cation complexes. It has been found that actinyl(V) cations form cation-cation complexes with a variety of cations, including actinyl(VI) cations. The radioactive nature of the actinide elements requires special handling techniques and also require limits be placed on the amount of material that can be used. The sensitivity of some oxidation states of the actinides to oxygen also presents a problem. Preliminary results will be presented for actinyl(V)-actinyl(VI) cation-cation complexes that were studied using a remote LIPAS system incorporating fiber optics for transmission of laser signals.

  4. Antisense oligodeoxynucleotide inhibition of a swelling-activated cation channel in osteoblast-like osteosarcoma cells.

    PubMed Central

    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. PMID:8700850

  5. 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.

  6. Dissolved organic nitrogen removal during water treatment by aluminum sulfate and cationic polymer coagulation.

    PubMed

    Lee, Wontae; Westerhoff, Paul

    2006-12-01

    Coagulation of three surface waters was conducted with aluminum salt and/or cationic polymer to assess dissolved organic nitrogen (DON) removal. Coagulation with aluminum sulfate removed equal or slightly lower amounts of DON as compared to dissolved organic carbon (DOC). At aluminum sulfate dosages up to 5mg per mg DOC, the cationic polymer improved DON removal by an additional 15% to 20% over aluminum sulfate alone. At very high aluminum sulfate dosages (>8 mg aluminum sulfate per mg DOC), however, the cationic polymer addition negligibly increased DON removal. Molecular weight fractionation before and after coagulation experiments indicated that cationic polymer addition can increase the removal of all molecular weight fractions of DON with the highest molecular weight fraction (>10,000 Da) being preferentially removed. Results indicated that the DON added as part of the cationic polymer was almost completely removed at optimum aluminum sulfate and polymer doses. PMID:17023020

  7. Electrochemical instability of solvent membranes during electrodialytic cation transport

    SciTech Connect

    Golubev, V.N.; Kontush, A.S.

    1987-08-01

    Experimental data are reported concerning the uptake of water by solvent membranes during dialysis and electrodialysis when the solvent is nonaqueous and a macrocyclic carrier is present. Aspects of the electrochemical instability of solvent membranes are discussed, and particularly the discontinuous conductivity fluctuations and the three stages of development of electric breakdown. The cationic selectivity of the macrocyclic carrier, the amount of water present in the solvent membrane, and the character of electrochemical instability of the membrane are shown to be interrelated.

  8. Copper cation removal in an electrokinetic cell containing zeolite.

    PubMed

    Elsayed-Ali, Omar H; Abdel-Fattah, Tarek; Elsayed-Ali, Hani E

    2011-01-30

    Zeolites are used in environmental remediation of soil or water to immobilize or remove toxic materials by cation exchange. An experiment was conducted to test the use a low electric field to direct the toxic cations towards the zeolite. An electrokinetic cell was constructed using carbon electrodes. Synthetic Linde Type A (LTA) zeolite was placed in the cell. Copper(II) chloride dissolved in water was used as a contaminant. The Cu(2+) concentration was measured for ten hours with and without an applied electric field. The removal of the Cu(2+) ions was accelerated by the applied field in the first two hours. For longer time, the electric field did not improve the removal rate of the Cu(2+) ions. The presence of zeolite and applied electric field complicates the chemistry near the cathode and causes precipitation of Cu(2+) ions as copper oxide on the surface of the zeolite. With increased electric field the zeolite farther away from the cathode had little cation exchange due to the higher drift velocity of the Cu(2+) ions. The results also show that, in the LTA Zeolite A pellets, the cation exchange of Cu is limited to a shell of several tens of micrometers. PMID:21109348

  9. Cationic nanoparticles induce nanoscale disruption in living cell plasma membranes.

    PubMed

    Chen, Jiumei; Hessler, Jessica A; Putchakayala, Krishna; Panama, Brian K; Khan, Damian P; Hong, Seungpyo; Mullen, Douglas G; Dimaggio, Stassi C; Som, Abhigyan; Tew, Gregory N; Lopatin, Anatoli N; Baker, James R; Holl, Mark M Banaszak; Orr, Bradford G

    2009-08-13

    It has long been recognized that cationic nanoparticles induce cell membrane permeability. Recently, it has been found that cationic nanoparticles induce the formation and/or growth of nanoscale holes in supported lipid bilayers. In this paper, we show that noncytotoxic concentrations of cationic nanoparticles induce 30-2000 pA currents in 293A (human embryonic kidney) and KB (human epidermoid carcinoma) cells, consistent with a nanoscale defect such as a single hole or group of holes in the cell membrane ranging from 1 to 350 nm(2) in total area. Other forms of nanoscale defects, including the nanoparticle porating agents adsorbing onto or intercalating into the lipid bilayer, are also consistent; although the size of the defect must increase to account for any reduction in ion conduction, as compared to a water channel. An individual defect forming event takes 1-100 ms, while membrane resealing may occur over tens of seconds. Patch-clamp data provide direct evidence for the formation of nanoscale defects in living cell membranes. The cationic polymer data are compared and contrasted with patch-clamp data obtained for an amphiphilic phenylene ethynylene antimicrobial oligomer (AMO-3), a small molecule that is proposed to make well-defined 3.4 nm holes in lipid bilayers. Here, we observe data that are consistent with AMO-3 making approximately 3 nm holes in living cell membranes. PMID:19606833

  10. Anti-inflammatory activity of cationic lipids.

    PubMed

    Filion, M C; Phillips, N C

    1997-10-01

    1. The effect of liposome phospholipid composition has been assumed to be relatively unimportant because of the presumed inert nature of phospholipids. 2. We have previously shown that cationic liposome formulations used for gene therapy inhibit, through their cationic component, the synthesis by activated macrophages of the pro-inflammatory mediators nitric oxide (NO) and tumour necrosis factor-alpha (TNF-alpha). 3. In this study, we have evaluated the ability of different cationic lipids to reduce footpad inflammation induced by carrageenan and by sheep red blood cell challenge. 4. Parenteral (i.p. or s.c) or local injection of the positively charged lipids dimethyldioctadecylammomium bromide (DDAB), dioleyoltrimethylammonium propane (DOTAP), dimyristoyltrimethylammonium propane (DMTAP) or dimethylaminoethanecarbamoyl cholesterol (DC-Chol) significantly reduced the inflammation observed in both models in a dose-dependent manner (maximum inhibition: 70-95%). 5. Cationic lipids associated with dioleyol- or dipalmitoyl-phosphatidylethanolamine retained their anti-inflammatory activity while cationic lipids associated with dipalmitoylphosphatidylcholine (DPPC) or dimyristoylphosphatidylglycerol (DMPG) showed no anti-inflammatory activity, indicating that the release of cationic lipids into the macrophage cytoplasm is a necessary step for anti-inflammatory activity. The anti-inflammatory activity of cationic lipids was abrogated by the addition of dipalmitoylphosphatidylethanolamine-poly(ethylene)glycol-2000 (DPPE-PEG2000) which blocks the interaction of cationic lipids with macrophages. 6. Because of the significant role of protein kinase C (PKC) in the inflammatory process we have determined whether the cationic lipids used in this study inhibit PKC activity. The cationic lipids significantly inhibited the activity of PKC but not the activity of a non-related protein kinase, PKA. The synthesis of interleukin-6 (IL-6), which is not dependent on PKC activity for its

  11. Selone-stabilized aryltellurenyl cations.

    PubMed

    Yadav, Sangeeta; Raju, Saravanan; Singh, Harkesh B; Butcher, Ray J

    2016-05-28

    Controlled bromination of a diarylditelluride, R2Te2 (R = 2,6-dimethylphenyl) (6) in dichloromethane led to the formation of a Te(II)-Te(IV) mixed-valent tellurenyl bromide, RBr2TeTeR (7). A further reaction of 7 with 1,3-dibutylbenzimidazolin-2-selone, C15H22N2Se (L) (9), produced the first selone adduct of the 2,6-dimethylphenyltellurenyl cation with the 2,6-dimethylphenyltellurium dibromide anion, [(2,6-Me2C6H3)Te(L)](+)[(2,6-Me2C6H3)TeBr2](-) (10). The red colored cationic adduct 10 is not stable in acetonitrile and disproportionated to give the selone adduct of 2,6-dimethylphenyltellurenyl bromide, [(2,6-Me2C6H3)Te(L)Br] (11b) and bis(2,6-dimethylphenyl)tellurium dibromide, [(2,6-Me2C6H3)2TeBr2], (13). The metathesis reaction of 11b with AgBF4 produced a stable dark red colored selone adduct of the 2,6-dimethylphenyltellurenyl cation with the BF4(-) anion, [(2,6-Me2C6H3)Te(L)](+)BF4(-) (15). The selone adducts of aryltellurenyl halides, i.e. [(2,6-Me2C6H3)Te(L)X] (X = Cl, Br, I) (11a-11c), have been synthesized by a one-pot reaction of 6 with an equimolar mixture of 9 and 1,3-dibutylbenzimidazolin-2-dihaloselones, C15H22N2SeX2 (14a-14c). Triphenylphosphine (PPh3), when treated with [(2,6-Me2C6H3)Te(L)X] (11a-11c), substitutes selone from the adduct to afford the triphenylphosphine adducts of aryltellurenyl halides, [(2,6-Me2C6H3)Te(PPh3)X] (16a-16c). PMID:27111528

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

    DOEpatents

    Wasserman, Stephen R.; Anderson, Kenneth B.; Song, Kang; Yuchs, Steven E.; Marshall, Christopher L.

    1998-01-01

    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.

  13. Electrical Conductivity.

    ERIC Educational Resources Information Center

    Allen, Philip B.

    1979-01-01

    Examines Drude's classical (1900) theory of electrical conduction, details the objections to and successes of the 1900 theory, and investigates the Quantum (1928) theory of conduction, reviewing its successes and limitations. (BT)

  14. Advancements in Anion Exchange Membrane Cations

    SciTech Connect

    Sturgeon, Matthew R.; Long, Hai; Park, Andrew M.; Pivovar, Bryan S.

    2015-10-15

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

  15. Tripodal Receptors for Cation and Anion Sensors

    PubMed Central

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

    2006-01-01

    This review discusses different types of artificial tripodal receptors for the selective recognition and sensing of cations and anions. Examples on the relationship between structure and selectivity towards cations and anions are described. Furthermore, their applications as potentiometric ion sensing are emphasised, along with their potential applications in optical sensors or optodes.

  16. Cationic Bolaamphiphiles for Gene Delivery

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

  17. Lithium ion conducting electrolytes

    DOEpatents

    Angell, C. Austen; Liu, Changle

    1996-01-01

    A liquid, predominantly lithium-conducting, ionic electrolyte having exceptionally high conductivity at temperatures of 100.degree. C. or lower, including room temperature, and comprising the lithium salts selected from the group consisting of the thiocyanate, iodide, bromide, chloride, perchlorate, acetate, tetrafluoroborate, perfluoromethane sulfonate, perfluoromethane sulfonamide, tetrahaloaluminate, and heptahaloaluminate salts of lithium, with or without a magnesium-salt selected from the group consisting of the perchlorate and acetate salts of magnesium. Certain of the latter embodiments may also contain molecular additives from the group of acetonitrile (CH.sub.3 CN) succinnonitrile (CH.sub.2 CN).sub.2, and tetraglyme (CH.sub.3 --O--CH.sub.2 --CH.sub.2 --O--).sub.2 (or like solvents) solvated to a Mg.sup.+2 cation to lower the freezing point of the electrolyte below room temperature. Other particularly useful embodiments contain up to about 40, but preferably not more than about 25, mol percent of a long chain polyether polymer dissolved in the lithium salts to provide an elastic or rubbery solid electrolyte of high ambient temperature conductivity and exceptional 100.degree. C. conductivity. Another embodiment contains up to about but not more than 10 mol percent of a molecular solvent such as acetone.

  18. Lithium ion conducting electrolytes

    DOEpatents

    Angell, C.A.; Liu, C.

    1996-04-09

    A liquid, predominantly lithium-conducting, ionic electrolyte is described having exceptionally high conductivity at temperatures of 100 C or lower, including room temperature, and comprising the lithium salts selected from the group consisting of the thiocyanate, iodide, bromide, chloride, perchlorate, acetate, tetrafluoroborate, perfluoromethane sulfonate, perfluoromethane sulfonamide, tetrahaloaluminate, and heptahaloaluminate salts of lithium, with or without a magnesium-salt selected from the group consisting of the perchlorate and acetate salts of magnesium. Certain of the latter embodiments may also contain molecular additives from the group of acetonitrile (CH{sub 3}CN), succinnonitrile (CH{sub 2}CN){sub 2}, and tetraglyme (CH{sub 3}--O--CH{sub 2}--CH{sub 2}--O--){sub 2} (or like solvents) solvated to a Mg{sup +2} cation to lower the freezing point of the electrolyte below room temperature. Other particularly useful embodiments contain up to about 40, but preferably not more than about 25, mol percent of a long chain polyether polymer dissolved in the lithium salts to provide an elastic or rubbery solid electrolyte of high ambient temperature conductivity and exceptional 100 C conductivity. Another embodiment contains up to about but not more than 10 mol percent of a molecular solvent such as acetone. 2 figs.

  19. Nitrogen-doped zirconia: A comparison with cation stabilized zirconia

    SciTech Connect

    Lee, Jong-Sook . E-mail: jong-sook.lee@fkf.mpg.de; Lerch, Martin; Maier, Joachim

    2006-01-15

    The conductivity behavior of nitrogen-doped zirconia is compared with that of zirconia doped with lower-valent cations and discussed in the framework of defect-defect interactions. While nominally introducing the same number of vacancies as yttrium, nitrogen dopants introduced in the anion sublattice of zirconia lead to substantially different defect kinetics and energetics. Compared to the equivalent yttrium doping nitrogen doping in the Y-Zr-O-N system substantially increases the activation energy and correspondingly decreases the conductivity at temperatures below 500{sup -}bar C in the vacancy range below 4mol%. The comparison of N-doped zirconia and zirconia systems doped with size-matched cation stabilizers, such as Sc, Yb and Y, shows that elastically driven vacancy-vacancy ordering interactions can phenomenologically account for the temperature- and composition-dependence. It is striking that materials with superior high-temperature conductivities due to weak dopant-vacancy interactions undergo severe deterioration at low temperature due to the strong vacancy-ordering. The analysis also explains qualitatively similar effects of Y co-doping in Yb-, Sc-, and N-doped zirconia. Small amount of Y in N-doped zirconia as well as in Sc-doped zirconia appears to hinder the formation of the long-range ordered phase and thus enhance the conductivity substantially.

  20. 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.

  1. Antibacterial properties of cationic steroid antibiotics.

    PubMed

    Savage, Paul B; Li, Chunhong; Taotafa, Uale; Ding, Bangwei; Guan, Qunying

    2002-11-19

    Cationic steroid antibiotics have been developed that display broad-spectrum antibacterial activity. These compounds are comprised of steroids appended with amine groups arranged to yield facially amphiphilic morphology. Examples of these antibiotics are highly bactericidal, while related compounds effectively permeabilize the outer membranes of Gram-negative bacteria sensitizing these organisms to hydrophobic antibiotics. Cationic steroid antibiotics exhibit various levels of eukaryote vs. prokaryote cell selectivity, and cell selectivity can be increased via charge recognition of prokaryotic cells. Studies of the mechanism of action of these antibiotics suggest that they share mechanistic aspects with cationic peptide antibiotics. PMID:12445638

  2. Lithium ion conducting ionic electrolytes

    DOEpatents

    Angell, C.A.; Xu, K.; Liu, C.

    1996-01-16

    A liquid, predominantly lithium-conducting, ionic electrolyte is described which has exceptionally high conductivity at temperatures of 100 C or lower, including room temperature. It comprises molten lithium salts or salt mixtures in which a small amount of an anionic polymer lithium salt is dissolved to stabilize the liquid against recrystallization. Further, a liquid ionic electrolyte which has been rubberized by addition of an extra proportion of anionic polymer, and which has good chemical and electrochemical stability, is described. This presents an attractive alternative to conventional salt-in-polymer electrolytes which are not cationic conductors. 4 figs.

  3. Lithium ion conducting ionic electrolytes

    DOEpatents

    Angell, C. Austen; Xu, Kang; Liu, Changle

    1996-01-01

    A liquid, predominantly lithium-conducting, ionic electrolyte is described which has exceptionally high conductivity at temperatures of 100.degree. C. or lower, including room temperature. It comprises molten lithium salts or salt mixtures in which a small amount of an anionic polymer lithium salt is dissolved to stabilize the liquid against recrystallization. Further, a liquid ionic electrolyte which has been rubberized by addition of an extra proportion of anionic polymer, and which has good chemical and electrochemical stability, is described. This presents an attractive alternative to conventional salt-in-polymer electrolytes which are not cationic conductors.

  4. Composite membranes prepared from cation exchange membranes and polyaniline and their transport properties in electrodialysis

    SciTech Connect

    Sata, Tshikatsu; Ishii, Yuuko; Kawamura, Kohei; Matsusaki, Koji

    1999-02-01

    A cation exchange membrane was modified with polyaniline by polymerizing aniline with ammonium peroxodisulfate on the membrane surfaces, producing a membrane with polyaniline layers on both surfaces or a membrane with a single polyaniline layer on the surface. The modified membranes, composite membranes, showed sodium ion permselectivity in electrodialysis compared with divalent cations at an optimum polymerization time. The electronic conductivity of dry membranes showed a maximum (ca. 5 {times} 10{sup {minus}3} S/cm) at the same polymerization time as the time to attain a maximum value of the sodium ion permselectivity. Because emeraldine-based polyaniline is conductive and has a cationic charge, the sodium ion permselectivity is based on the difference in the electrostatic repulsion forces of the cationic charge on the membrane surface of a desalting side to divalent cations and sodium ions. In fact, the selective permeation of sodium ions appeared only when the layer faced the desalting side of the membrane, and was affected by dissociation of polyaniline. Further oxidized polyaniline, pernigraniline-based polyaniline, did not affect the permselectivity between cations, and the diffusion coefficient of neutral molecules, urea, increased with increasing polymerization time. Sodium ion permselectivity was maintained with repeated electrodialysis.

  5. Ion selectivity of colicin E1: II. Permeability to organic cations.

    PubMed

    Bullock, J O; Kolen, E R; Shear, J L

    1992-05-01

    Channels formed by colicin E1 in planar lipid bilayers have large diameters and conduct both cations and anions. The rates at which ions are transported, however, are relatively slow, and the relative anion-to-cation selectivity is modulated over a wide range by the pH of the bathing solutions. We have examined the permeability of these channels to cationic probes having a variety of sizes, shapes, and charge distributions. All of the monovalent probes were found to be permeant, establishing a minimum diameter at the narrowest part of the pore of approximately 9 A. In contrast to this behavior, all of the polyvalent organic cations were shown to be impermeant. This simple exclusionary rule is interpreted as evidence that, when steric restrictions require partial dehydration of an ion, the structure of the channel is able to provide a substitute electrostatic environment for only one charged group at time. PMID:1380089

  6. Preparation, characterization, and efficient transfection of cationic liposomes and nanomagnetic cationic liposomes

    PubMed Central

    Samadikhah, Hamid Reza; Majidi, Asia; Nikkhah, Maryam; Hosseinkhani, Saman

    2011-01-01

    Purpose Cationic liposomes (CLs) are composed of phospholipid bilayers. One of the most important applications of these particles is in drug and gene delivery. However, using CLs to deliver therapeutic nucleic acids and drugs to target organs has some problems, including low transfection efficiency in vivo. The aim of this study was to develop novel CLs containing magnetite to overcome the deficiencies. Materials and methods CLs and magnetic cationic liposomes (MCLs) were prepared using the freeze-dried empty liposome method. Luciferase-harboring vectors (pGL3) were transferred into liposomes and the transfection efficiencies were determined by luciferase assay. Firefly luciferase is one of most popular reporter genes often used to measure the efficiency of gene transfer in vivo and in vitro. Different formulations of liposomes have been used for delivery of different kinds of gene reporters. Lipoplex (liposome–plasmid DNA complexes) formation was monitored by gel retardation assay. Size and charge of lipoplexes were determined using particle size analysis. Chinese hamster ovary cells were transfected by lipoplexes (liposome-pGL3); transfection efficiency and gene expression level was evaluated by luciferase assay. Results High transfection efficiency of plasmid by CLs and novel nanomagnetic CLs was achieved. Moreover, lipoplexes showed less cytotoxicity than polyethyleneimine and Lipofectamine™. Conclusion Novel liposome compositions (1,2-dipalmitoyl-sn-glycero-3-phosphocholine [DPPC]/dioctadecyldimethylammonium bromide [DOAB] and DPPC/cholesterol/DOAB) with high transfection efficiency can be useful in gene delivery in vitro. MCLs can also be used for targeted gene delivery, due to magnetic characteristic for conduction of genes or drugs to target organs. PMID:22072865

  7. SLO2 Channels Are Inhibited by All Divalent Cations That Activate SLO1 K+ Channels.

    PubMed

    Budelli, Gonzalo; Sun, Qi; Ferreira, Juan; Butler, Alice; Santi, Celia M; Salkoff, Lawrence

    2016-04-01

    Two members of the family of high conductance K(+)channels SLO1 and SLO2 are both activated by intracellular cations. However, SLO1 is activated by Ca(2+)and other divalent cations, while SLO2 (Slack or SLO2.2 from rat) is activated by Na(+) Curiously though, we found that SLO2.2 is inhibited by all divalent cations that activate SLO1, with Zn(2+)being the most effective inhibitor with an IC50of ∼8 μmin contrast to Mg(2+), the least effective, with an IC50of ∼ 1.5 mm Our results suggest that divalent cations are not SLO2 pore blockers, but rather inhibit channel activity by an allosteric modification of channel gating. By site-directed mutagenesis we show that a histidine residue (His-347) downstream of S6 reduces inhibition by divalent cations. An analogous His residue present in some CNG channels is an inhibitory cation binding site. To investigate whether inhibition by divalent cations is conserved in an invertebrate SLO2 channel we cloned the SLO2 channel fromDrosophila(dSLO2) and compared its properties to those of rat SLO2.2. We found that, like rat SLO2.2, dSLO2 was also activated by Na(+)and inhibited by divalent cations. Inhibition of SLO2 channels in mammals andDrosophilaby divalent cations that have second messenger functions may reflect the physiological regulation of these channels by one or more of these ions. PMID:26823461

  8. Cationic nanoemulsions as potential carriers for intracellular delivery.

    PubMed

    Khachane, P V; Jain, A S; Dhawan, V V; Joshi, G V; Date, A A; Mulherkar, R; Nagarsenker, M S

    2015-04-01

    Successful cytosolic delivery enables opportunities for improved treatment of various genetic disorders, infectious diseases and cancer. Cationic nanoemulsions were designed using alternative excipients and evaluated for particle size, charge, effect of sterilization on its stability, DNA condensation potential and cellular uptake efficiency. Various concentrations of non-ionic and ionic stabilizers were evaluated to design formula for colloidally stable cationic nanoemulsion. The nanoemulsion comprised of 5% Capmul MCM, 0.5% didodecyldimethylammonium bromide (DDAB), 1% phospholipid, 1% Poloxamer 188 and 2.25% glycerol and possessed particle size of 81.6 ± 3.56 nm and 137.1 ± 1.57 nm before and after steam sterilization, respectively. DNA condensation studies were carried out at various nanoemulsion: DNA ratios ranging from 1:1 to 10:1. Cell uptake studies were conducted on human embryonic kidney (HEK) cell lines which are widely reported for transfection studies. The nanoemulsions showed excellent cellular uptake as evaluated by fluorescence microscopy and flow cytometry. Overall, a colloidally stable cationic nanoemulsion with good DNA condensation ability was successfully fabricated for efficient cytosolic delivery and potential for in vivo effectiveness. PMID:25972740

  9. Cation-cation clusters in ionic liquids: Cooperative hydrogen bonding overcomes like-charge repulsion

    PubMed Central

    Knorr, Anne; Ludwig, Ralf

    2015-01-01

    Direct spectroscopic evidence for H-bonding between like-charged ions is reported for the ionic liquid, 1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate. New infrared bands in the OH frequency range appear at low temperatures indicating the formation of H-bonded cation-cation clusters similar to those known for water and alcohols. Supported by DFT calculations, these vibrational bands can be assigned to attractive interaction between the hydroxyl groups of the cations. The repulsive Coulomb interaction is overcome by cooperative hydrogen bonding between ions of like charge. The transition energy from purely cation-anion interacting configurations to those including cation-cation H-bonds is determined to be 3–4 kJmol−1. The experimental findings and DFT calculations strongly support the concept of anti-electrostatic hydrogen bonds (AEHBs) as recently suggested by Weinhold and Klein. The like-charge configurations are kinetically stabilized with decreasing temperatures. PMID:26626928

  10. Test procedure for cation exchange chromatography

    SciTech Connect

    Cooper, T.D.

    1994-08-24

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

  11. Stretch-activated cation channel from larval bullfrog skin.

    PubMed

    Hillyard, Stanley D; Willumsen, Niels J; Marrero, Mario B

    2010-05-01

    Cell-attached patches from isolated epithelial cells from larval bullfrog skin revealed a cation channel that was activated by applying suction (-1 kPa to -4.5 kPa) to the pipette. Activation was characterized by an initial large current spike that rapidly attenuated to a stable value and showed a variable pattern of opening and closing with continuing suction. Current-voltage plots demonstrated linear or inward rectification and single channel conductances of 44-56 pS with NaCl or KCl Ringer's solution as the pipette solution, and a reversal potential (-V(p)) of 20-40 mV. The conductance was markedly reduced with N-methyl-D-glucamide (NMDG)-Cl Ringer's solution in the pipette. Neither amiloride nor ATP, which are known to stimulate an apical cation channel in Ussing chamber preparations of larval frog skin, produced channel activation nor did these compounds affect the response to suction. Stretch activation was not affected by varying the pipette concentrations of Ca(2+) between 0 mmol l(-1) and 4 mmol l(-1) or by varying pH between 6.8 and 8.0. However, conductance was reduced with 4 mmol l(-1) Ca(2+). Western blot analysis of membrane homogenates from larval bullfrog and larval toad skin identified proteins that were immunoreactive with mammalian TRPC1 and TRPC5 (TRPC, canonical transient receptor potential channel) antibodies while homogenates of skin from newly metamorphosed bullfrogs were positive for TRPC1 and TRPC3/6/7 antibodies. The electrophysiological response of larval bullfrog skin resembles that of a stretch-activated cation channel characterized in Xenopus oocytes and proposed to be TRPC1. These results indicate this channel persists in all life stages of anurans and that TRP isoforms may be important for sensory functions of their skin. PMID:20435829

  12. 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.

  13. Conduct disorder

    MedlinePlus

    Disruptive behavior - child; Impulse control problem - child ... Conduct disorder has been linked to: Child abuse Drug or alcohol abuse in the parents Family conflicts Genetic defects Poverty The diagnosis is more common among boys. It is ...

  14. Electrical Conductivity.

    ERIC Educational Resources Information Center

    Hershey, David R.; Sand, Susan

    1993-01-01

    Explains how electrical conductivity (EC) can be used to measure ion concentration in solutions. Describes instrumentation for the measurement, temperature dependence and EC, and the EC of common substances. (PR)

  15. Spectroscopic evidence of 'jumping and pecking' of cholinium and H-bond enhanced cation-cation interaction in ionic liquids.

    PubMed

    Knorr, Anne; Fumino, Koichi; Bonsa, Anne-Marie; Ludwig, Ralf

    2015-12-14

    The subtle energy-balance between Coulomb-interaction, hydrogen bonding and dispersion forces governs the unique properties of ionic liquids. To measure weak interactions is still a challenge. This is in particular true in the condensed phase wherein a melange of different strong and directional types of interactions is present and cannot be detected separately. For the ionic liquids (2-hydroxyethyl)-trimethylammonium (cholinium) bis(trifluoro-methylsulfonyl)amide and N,N,N-trimethyl-N-propylammonium bis(trifluoromethylsulfonyl)amide which differ only in the 2-hydroxyethyl and the propyl groups of the cations, we could directly observe distinct vibrational signatures of hydrogen bonding between the cation and the anion indicated by 'jumping and pecking' motions of cholinium. The assignment could be confirmed by isotopic substitution H/D at the hydroxyl group of cholinium. For the first time we could also find direct spectroscopic evidence for H-bonding between like-charged ions. The repulsive Coulomb interaction between the cations is overcome by cooperative hydrogen bonding between the 2-hydroxyethyl functional groups of cholinium. This H-bond network is reflected in the properties of protic ionic liquids (PILs) such as viscosities and conductivities. PMID:26292169

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

    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.

  17. High cation transport polymer electrolyte

    DOEpatents

    Gerald, II, Rex E.; Rathke, Jerome W.; Klingler, Robert J.

    2007-06-05

    A solid state ion conducting electrolyte and a battery incorporating same. The electrolyte includes a polymer matrix with an alkali metal salt dissolved therein, the salt having an anion with a long or branched chain having not less than 5 carbon or silicon atoms therein. The polymer is preferably a polyether and the salt anion is preferably an alkyl or silyl moiety of from 5 to about 150 carbon/silicon atoms.

  18. Mechanism of oligonucleotide release from cationic liposomes.

    PubMed Central

    Zelphati, O; Szoka, F C

    1996-01-01

    We propose a mechanism for oligonucleotide (ODN) release from cationic lipid complexes in cells that accounts for various observations on cationic lipid-nucleic acid-cell interactions. Fluorescent confocal microscopy of cells treated with rhodamine-labeled cationic liposome/ fluorescein-labeled ODN (F-ODN) complexes show the F-ODN separates from the lipid after internalization and enters the nucleus leaving the fluorescent lipid in cytoplasmic structures. ODN displacement from the complex was studied by fluorescent resonance energy transfer. Anionic liposome compositions (e.g., phosphatidylserine) that mimic the cytoplasmic facing monolayer of the cell membrane released ODN from the complex at about a 1:1 (-/+) charge ratio. Release was independent of ionic strength and pH. Physical separation of the F-ODN from monovalent and multivalent cationic lipids was confirmed by gel electrophoresis. Fluid but not solid phase anionic liposomes are required, whereas the physical state of the cationic lipids does not effect the release. Water soluble molecules with a high negative linear charge density, dextran sulfate, or heparin also release ODN. However, ATP, spermidine, spermine, tRNA, DNA, polyglutamic acid, polylysine, bovine serum albumin, or histone did not release ODN, even at 100-fold charge excess (-/+). Based upon these results, we propose that the complex, after internalization by endocytosis, induces flip-flop of anionic lipids from the cytoplasmic facing monolayer. Anionic lipids laterally diffuse into the complex and form a charged neutralized ion-pair with the cationic lipids. This leads to displacement of the ODN from the cationic lipid and its release into the cytoplasm. Images Fig. 1 Fig. 3 PMID:8876163

  19. New ester based gemini surfactants: the effect of different cationic headgroups on micellization properties and viscosity of aqueous micellar solution.

    PubMed

    Bhadani, Avinash; Tani, Misako; Endo, Takeshi; Sakai, Kenichi; Abe, Masahiko; Sakai, Hideki

    2015-07-15

    A new series of ester functionalized cationic gemini surfactants having different cationic headgroups (i.e. piperidinium, pyrrolidinium, morpholinium and quaternary ammonium) have been synthesized and characterized using NMR and Mass spectroscopy. These new gemini surfactants were investigated for their micellization and viscosity properties using surface tension, conductivity, fluorescence and rheology thechniques. The physicochemical properties of the aqueous surfactant system were influenced by polarity, size and the nature of cationic headgroups as the surface, thermodynamic and viscosity properties of these gemini surfactants were found to be dependent on the type of cationic headgroup. The current research finding establishes the structure-property relationship of the surfactant molecule specifically taking into account the dominant role displayed by the nature of the cationic headgroup. PMID:26145125

  20. Physical Properties of Ionic Liquids Consisting of the 1-Butyl-3-Methylimidazolium Cation with Various Anions and the Bis(trifluoromethylsulfonyl)imide Anion with Various Cations

    SciTech Connect

    Jin, Hui; O'Hare, Bernie; Dong, Jing; Arzhantsev, Sergei; Baker, Gary A; Wishart, James F.; Benesi, Alan; Maroncelli, Mark

    2008-01-01

    Physical properties of 4 room-temperature ionic liquids consisting of the 1-butyl-3-methylimidazolium cation with various perfluorinated anions and the bis(trifluoromethylsulfonyl)imide (Tf2N-) anion with 12 pyrrolidinium-, ammonium-, and hydroxyl-containing cations are reported. Electronic structure methods are used to calculate properties related to the size, shape, and dipole moment of individual ions. Experimental measurements of phase-transition temperatures, densities, refractive indices, surface tensions, solvatochromic polarities based on absorption of Nile Red, 19F chemical shifts of the Tf2N- anion, temperature-dependent viscosities, conductivities, and cation diffusion coefficients are reported. Correlations among the measured quantities as well as the use of surface tension and molar volume for estimating Hildebrand solubility parameters of ionic liquids are also discussed.

  1. Appropriate Conduct

    ERIC Educational Resources Information Center

    Di Lullo, Louis

    2004-01-01

    Many years ago when the author assumed the role of assistant principal for school climate, discipline, and attendance, he inherited many school policies and guidelines that were outdated, unfair, and without merit in the current school climate. Because the school conduct code had not been revised since the school opened in 1960, many of the…

  2. Conducting Meetings.

    ERIC Educational Resources Information Center

    United Tribes Educational Technical Center, Bismarck, ND.

    Written for anyone interested in what makes a meeting run smoothly (and what doesn't), the guide for conducting meetings is divided into the following sections: the chairperson (his/her responsibilities, preparing an agenda, organizing discussions); the meeting (quorums, discussions, points of order, and clarification); the motion (making the…

  3. Innate cation sensitivity in a semiconducting polymer.

    PubMed

    Althagafi, Talal M; Algarni, Saud A; Grell, Martin

    2016-09-01

    Water-gated organic thin film transistors (OTFTs) using the hole transporting semiconducting polymer, poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT), show an innate response of their threshold voltage to the addition of divalent metal cations to the gating water, without deliberately introducing an ion-sensitive component. A similar threshold response is shown for several divalent cations, but is absent for monovalent cations. Response is absent for transistors using the inorganic semiconductor ZnO, or the similar organic semiconductor poly(3-hexylthiophene) (rrP3HT), instead of PBTTT. We assign innate cation sensitivity to residues of the organometallic Pd(0) complex used as catalyst in PBTTT synthesis which bears strong resemblance to typical metal chelating agents. Organometallic Pd(0) residues are absent from ZnO, and also from rrP3HT which is polymerised with a different type of catalyst. However, when Pd(0) complex is deliberately added to rrP3HT casting solutions, resulting OTFTs also display threshold response to a divalent cation. PMID:27343580

  4. Cation-pi interactions as a mechanism in technical lignin adsorption to cationic surfaces.

    PubMed

    Pillai, Karthik V; Renneckar, Scott

    2009-04-13

    The assembly of dissolved technical lignins in aqueous and organic medium has been studied at the solid-liquid interface. Adsorption of alkali lignin onto gold coated crystals treated with a cationic polymer was determined using a quartz crystal microbalance with dissipation monitoring. Complete coverage of the cationic surface with alkali lignin occurred at low solution concentration, revealing a high affinity coefficient under both alkali and neutral conditions. With additional adsorption studies from organosolv lignin in organic solvent and spectroscopic analysis of mixtures of cationic polymer and alkali lignin, a noncovalent interaction between lignin's aromatic rings and the cation of the quaternary ammonium group was shown to exist. The work underscores how polyphenolic biopolymers can strongly interact with cations through noncovalent interactions to control molecular architecture. PMID:19226174

  5. Impermeability of the GIRK2 weaver channel to divalent cations.

    PubMed

    Hou, P; Di, A; Huang, P; Hansen, C B; Nelson, D J

    2000-05-01

    A single amino acid mutation (G156S) in the putative pore-forming region of the G protein-sensitive, inwardly rectifying K(+) channel subunit, GIRK2, renders the conductance constitutively active and nonselective for monovalent cations. The mutant channel subunit (GIRK2wv) causes the pleiotropic weaver disease in mice, which is characterized by the selective vulnerability of cerebellar granule cells and Purkinje cells, as well as dopaminergic neurons in the mesencephalon, to cell death. It has been proposed that divalent cation permeability through constitutively active GIRK2wv channels contributes to a rise in internal calcium in the GIRK2wv-expressing neurons, eventually leading to cell death. We carried out comparative studies of recombinant GIRK2wv channels expressed in Xenopus oocytes and COS-7 cells to determine the magnitude and relative permeability of the GIRK2wv conductance to Ca(2+). Data from these studies demonstrate that the properties of the expressed current differ in the two systems and that when recombinant GIRK2wv is expressed in mammalian cells it is impermeable to Ca(2+). PMID:10794678

  6. Electrodeless conductivity.

    PubMed

    Light, T S; McHale, E J; Fletcher, K S

    1989-01-01

    Electrodeless conductivity is a technique for measuring the concentration of electrolytes in solution and utilizes a probe consisting of two toroids in close proximity, both of which are immersed in the solution. In special cases, the toroids may be mounted externally on insulated pipes carrying the solution. One toroid radiates an alternating electric field in the audiofrequency range and the other acts as a receiver to pick up the small current induced by the ions moving in a conducting loop of solution. Coatings which would foul contacting electrodes, such as suspensions, precipitates or oil, have little or no effect. Applications are chiefly to continuous measurement in the chemical processing industries, including pulp and paper, mining and heavy chemical production. The principles and practical details of the method are reviewed and cell-diameter, wall, and temperature effects are discussed. PMID:18964695

  7. Heat conduction

    SciTech Connect

    Lilley, D.G.

    1987-01-01

    Analytical and numerical methods, including both finite difference and finite element techniques, are presented with applications to heat conduction problems. Numerical and analytical methods are integrated throughout the text and a variety of complexities are thoroughly treated with many problems, solutions and computer programs. This book is presented as a fundamental course suitable for senior undergraduate and first year graduate students, with end-of-chapter problems and answers included. Sample case studies and suggested projects are included.

  8. Conduction apraxia.

    PubMed

    Ochipa, C; Rothi, L J; Heilman, K M

    1994-10-01

    A left hemisphere damaged patient with ideomotor apraxia is described, whose performance on pantomime to verbal command was superior to pantomime imitation. His reception of these same gestures (gesture naming) was spared. This syndrome has been named conduction apraxia. To account for this selective impaired performance on gesture imitation, a separation of the representations for gesture production and reception is proposed and a non-lexical gesture processing route for gesture imitation is suggested. PMID:7931387

  9. 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

  10. Solution of trivalent cations into uranium dioxide

    NASA Astrophysics Data System (ADS)

    Middleburgh, S. C.; Parfitt, D. C.; Grimes, R. W.; Dorado, B.; Bertolus, M.; Blair, P. R.; Hallstadius, L.; Backman, K.

    2012-01-01

    The accommodation of trivalent oxides (M 2O 3) in uranium dioxide has been investigated using atomic scale simulation. Calculations suggest that all trivalent oxides studied preferentially enter UO 2 by associating the substitutional ion with an oxygen vacancy, larger cations forming the cluster {2MU':VOrad rad }×. Solution into hyper-stoichiometric UO 2+ x was accompanied by the formation of the {MU':UUrad }× cluster and smaller solution energies than into stoichiometric UO 2. Solubility is a particularly strong function of hyper-stoichiometry for smaller cations such as Cr 3+, which has implications for the use of Cr 2O 3 as a grain enlarger but not so for larger cations such s Gd 3+.

  11. Cationic Lipid-Based Nucleic Acid Vectors.

    PubMed

    Jubeli, Emile; Goldring, William P D; Pungente, Michael D

    2016-01-01

    The delivery of nucleic acids into cells remains an important laboratory cell culture technique and potential clinical therapy, based upon the initial cellular uptake, then translation into protein (in the case of DNA), or gene deletion by RNA interference (RNAi). Although viral delivery vectors are more efficient, the high production costs, limited cargo capacity, and the potential for clinical adverse events make nonviral strategies attractive. Cationic lipids are the most widely applied and studied nonviral vectors; however, much remains to be solved to overcome limitations of these systems. Advances in the field of cationic lipid-based nucleic acid (lipoplex) delivery rely upon the development of robust and reproducible lipoplex formulations, together with the use of cell culture assays. This chapter provides detailed protocols towards the formulation, delivery, and assessment of in vitro cationic lipid-based delivery of DNA. PMID:27436310

  12. Dimethyl sulfoxide at high concentrations inhibits non-selective cation channels in human erythrocytes.

    PubMed

    Nardid, Oleg A; Schetinskey, Miroslav I; Kucherenko, Yuliya V

    2013-03-01

    Dimethyl sulfoxide (DMSO), a by-product of the pulping industry, is widely used in biological research, cryobiology and medicine. On cellular level DMSO was shown to suppress NMDA-AMPA channels activation, blocks Na+ channel activation and attenuates Ca2+ influx (Lu and Mattson 2001). In the present study we explored the whole-cell patch-clamp to examine the acute effect of high concentrations of DMSO (0.1-2 mol/l) on cation channels activity in human erythrocytes. Acute application of DMSO (0.1-2 mol/l) dissolved in Cl--containing saline buffer solution significantly inhibited cation conductance in human erythrocytes. Inhibition was concentration-dependent and had an exponential decay profile. DMSO (2 mol/l) induced cation inhibition in Cl-- containing saline solutions of: 40.3 ± 3.9% for K+, 35.4 ± 3.1% for Ca2+ and 47.4 ± 1.9% for NMDG+. Substitution of Cl- with gluconate- increased the inhibitory effect of DMSO on the Na+ current. Inhibitory effect of DMSO was neither due to high permeability of erythrocytes to DMSO nor to an increased tonicity of the bath media since no effect was observed in 2 mol/l glycerol solution. In conclusion, we have shown that high concentrations of DMSO inhibit the non-selective cation channels in human erythrocytes and thus protect the cells against Na+ and Ca2+ overload. Possible mechanisms of DMSO effect on cation conductance are discussed. PMID:23531832

  13. IN-SERVICE HYDRAULIC CONDUCTIVITY OF GCLS IN LANDFILL COVERS - LABORATORY AND FIELD STUDIES

    EPA Science Inventory

    Laboratory experiments using multi-species inorganic solutions (containing calcium and sodium) were conducted on specimens of a new geosynthetic clay liner (GCL) containing sodium bentonite to determine how cation exchange and desiccation affected the hydraulic conductivity. Calc...

  14. Cationically polymerizable monomers derived from renewable sources

    SciTech Connect

    Crivello, J.V.

    1992-10-01

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

  15. ABSORPTION METHOD FOR SEPARATING METAL CATIONS

    DOEpatents

    Tompkins, E.R.; Parker, G.W.

    1959-03-10

    An improved method is presented for the chromatographic separation of fission products wherein a substantial reduction in liquid volume is obtained. The process consists in contacting a solution containing fission products with a body of ion-exchange adsorbent to effect adsorption of fission product cations. The loaded exchange resin is then contacted with a small volume of a carboxylic acid eluant, thereby recovering the fission products. The fission product carrying eluate is acidified without increasing its volume to the volume of the original solution, and the acidified eluate is then used as a feed solution for a smaller body of ion-exchange resin effecting readsorption of the fission product cations.

  16. 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.

  17. Conductivity Probe

    NASA Technical Reports Server (NTRS)

    2008-01-01

    The Thermal and Electrical Conductivity Probe (TECP) for NASA's Phoenix Mars Lander took measurements in Martian soil and in the air.

    The needles on the end of the instrument were inserted into the Martian soil, allowing TECP to measure the propagation of both thermal and electrical energy. TECP also measured the humidity in the surrounding air.

    The needles on the probe are 15 millimeters (0.6 inch) long.

    The Phoenix Mission is led by the University of Arizona, Tucson, on behalf of NASA. Project management of the mission is by NASA's Jet Propulsion Laboratory, Pasadena, Calif. Spacecraft development is by Lockheed Martin Space Systems, Denver.

  18. 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. PMID:26460827

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

    SciTech Connect

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

    1996-12-31

    The problems associated with the disposal of toxic metals in an environmentally acceptable manner continues to plague industry. Such metals as nickel, vanadium, molybdenum, cobalt, iron, and antimony present physiological and ecological challenges that are best addressed through minimization of exposure and dispersion. 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.

  20. 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

  1. Viscoelastic cationic polymers containing the urethane linkage

    NASA Technical Reports Server (NTRS)

    Rembaum, A. (Inventor)

    1972-01-01

    A method for the synthesis and manufacturing of elastomeric compositions and articles containing quaternary nitrogen centers and condensation residues along the polymeric backbone of the centers is presented. Linear and cross-linked straight chain and block polymers having a wide damping temperature range were synthesized. Formulae for the viscoelastic cationic polymers are presented.

  2. ADSORPTION OF ORGANIC CATIONS TO NATURAL MATERIALS

    EPA Science Inventory

    The factors that control the extent of adsorption of amphiphilic organic cations on environmental and pristine surfaces have been studied. he sorbents were kaolinite, montmorillonite, two aquifer materials, and a soil; solutions contained various concentrations of NaCl and CaC12,...

  3. Dynamics of poly(4-hydroxystyrene) radical cation

    NASA Astrophysics Data System (ADS)

    Okamoto, Kazumasa; Kozawa, Takahiro; Tagawa, Seiichi

    2008-03-01

    Poly(4-hydroxystyrene) (PHS) has been used in KrF excimer laser (248 nm) lithography as a backbone polymer, and is also a promising material for EUV or electron beam lithography. Analysis of the intermediate species is important for the control of reactions in resist materials. Since the size of integrated circuits fabricated for mass production will decrease below 30 nm and the size error must also be decreased to the molecular level, the elucidation of proton dynamics at the molecular level is also important for reducing the deviation of the resist pattern size. In this study, the dynamics of PHS radical cations were studied, because PHS radical cation is main source of proton. The transient absorption of PHS was observed in the near-infrared region (NIR) in p-dioxane solutions by pulse radiolysis. The intramolecular PHS dimer radical cation (M2 +.) were observed, whereas p-cresol shows no distinct CR band. Although the radical cations of phenol derivatives are known to be easily deprotonated, it was found that M2 +. formation prevents deprotonation by its charge resonance stabilization.

  4. ADSORPTION OF ORGANIC CATIONS TO NATURAL MATERIALS

    EPA Science Inventory

    The factors that control the extent of adsorption of amphiphilic organic cations on environmental and pristine surfaces have been studied. The sorbents were kaolinite, montmorillonite, two aquifer materials, and a soil; solutions contained various concentrations of NaCl and CaCl,...

  5. 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.

  6. 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.

  7. Surfactant properties of ionic liquids containing short alkyl chain imidazolium cations and ibuprofenate anions.

    PubMed

    Tourné-Péteilh, Corine; Devoisselle, Jean-Marie; Vioux, André; Judeinstein, Patrick; In, Martin; Viau, Lydie

    2011-09-14

    Interfacial tension, electrical conductivity, NMR self-diffusion and DLS experiments have been used to investigate the self-aggregation in water of ionic liquids associating an ibuprofenate anion and 1-alkyl-3-methylimidazolium [C(n)MIm](+) (n = 4, 6, 8) cations. Despite the short alkyl chain on imidazolium cations (n ≤ 8), these ionic liquids exhibit particularly low Critical Aggregation Concentrations (CAC), significantly lower than their parent 1-alkyl-3-methylimidazolium chloride salts. This behaviour is attributed to the formation of catanionic pairs between ibuprofenate and imidazolium. PMID:21799958

  8. Solvent extraction of lanthanoid picrates with crown ethers: preferential sandwich complexation and unique cation selectivities

    SciTech Connect

    Nakagawa, K.; Okada, S.; Inoue, Y.; Tai, A.; Hakushi, T.

    1988-11-15

    Quantitative solvent extractions of aqueous lanthanoid picrates with 15-crown-5 and 18-crown-6 were conducted at low ionic strength in the absence of background salts. An overwhelming preference for the sandwich complexation and unique cation selectivities were observed. The peak extraction constants were found for samarium with 15-crown-5 (1:2 stoichiometry) and for cerium and praseodymium with 18-crown-6 (1:1 and 1:2 stoichiometries, respectively). The facile sandwich complexation and unique cation selectivities are interpreted in terms of the heavy hydration of lanthanoid ions of high charge density.

  9. Dendritic Cells Stimulated by Cationic Liposomes.

    PubMed

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

    2016-01-01

    Immunotherapy of cancer aims to harness the immune system to detect and destroy cancer cells. To induce an immune response against cancer, activated dendritic cells (DCs) must present tumor antigens to T lymphocytes of patients. However, cancer patients' DCs are frequently defective, therefore, they are prone to induce rather tolerance than immune responses. In this context, loading tumor antigens into DCs and, at the same time, activating these cells, is a tempting goal within the field. Thus, we investigated the effects of cationic liposomes on the DCs differentiation/maturation, evaluating their surface phenotype and ability to stimulate T lymphocytes proliferation in vitro. The cationic liposomes composed by egg phosphatidylcholine, 1,2-dioleoyl-3-trimethylammonium propane and 1,2-dioleoylphosphatidylethanolamine (50/25/25% molar) were prepared by the thin film method followed by extrusion (65 nm, polydispersity of 0.13) and by the dehydration-rehydration method (95% of the population 107 nm, polydispersity of 0.52). The phenotypic analysis of dendritic cells and the analysis of T lymphocyte proliferation were performed by flow cytometry and showed that both cationic liposomes were incorporated and activated dendritic cells. Extruded liposomes were better incorporated and induced higher CD86 expression for dendritic cells than dehydrated-rehydrated vesicles. Furthermore, dendritic cells which internalized extruded liposomes also provided stronger T lymphocyte stimulation. Thus, cationic liposomes with a smaller size and polydispersity seem to be better incorporated by dendritic cells. Hence, these cationic liposomes could be used as a potential tool in further cancer immunotherapy strategies and contribute to new strategies in immunotherapy. PMID:27398454

  10. Silica-based cationic bilayers as immunoadjuvants

    PubMed Central

    Lincopan, Nilton; Santana, Mariana RA; Faquim-Mauro, Eliana; da Costa, Maria Helena B; Carmona-Ribeiro, Ana M

    2009-01-01

    Background Silica particles cationized by dioctadecyldimethylammonium bromide (DODAB) bilayer were previously described. This work shows the efficiency of these particulates for antigen adsorption and presentation to the immune system and proves the concept that silica-based cationic bilayers exhibit better performance than alum regarding colloid stability and cellular immune responses for vaccine design. Results Firstly, the silica/DODAB assembly was characterized at 1 mM NaCl, pH 6.3 or 5 mM Tris.HCl, pH 7.4 and 0.1 mg/ml silica over a range of DODAB concentrations (0.001–1 mM) by means of dynamic light scattering for particle sizing and zeta-potential analysis. 0.05 mM DODAB is enough to produce cationic bilayer-covered particles with good colloid stability. Secondly, conditions for maximal adsorption of bovine serum albumin (BSA) or a recombinant, heat-shock protein from Mycobacterium leprae (18 kDa-hsp) onto DODAB-covered or onto bare silica were determined. At maximal antigen adsorption, cellular immune responses in vivo from delayed-type hypersensitivity reactions determined by foot-pad swelling tests (DTH) and cytokines analysis evidenced the superior performance of the silica/DODAB adjuvant as compared to alum or antigens alone whereas humoral response from IgG in serum was equal to the one elicited by alum as adjuvant. Conclusion Cationized silica is a biocompatible, inexpensive, easily prepared and possibly general immunoadjuvant for antigen presentation which displays higher colloid stability than alum, better performance regarding cellular immune responses and employs very low, micromolar doses of cationic and toxic synthetic lipid. PMID:19152701

  11. Mixed-valent neptunium(IV/V) compound with cation-cation-bound six-membered neptunyl rings.

    PubMed

    Jin, Geng Bang

    2013-11-01

    A new mixed-valent neptunium(IV/V) compound has been synthesized by evaporation of a neptunium(V) acidic solution. The structure of the compound features cation-cation-bound six-membered neptunyl(V) rings. These rings are further connected by Np(IV) ions through cation-cation interactions (CCIs) into a three-dimensional neptunium cationic open framework. This example illustrates the possibility of isolating neptunyl(V) CCI oligomers in inorganic systems using other cations to compete with Np(V) in bonding with the neptunyl oxygen. PMID:24187926

  12. Human skin is permselective for the small, monovalent cations sodium and potassium but not for nickel and chromium.

    PubMed

    La Count, Terri D; Kasting, Gerald B

    2013-07-01

    The molar conductance of excised human skin (Λ(skin)) immersed in electrolyte solutions comprising four cationic (Na(+), K(+), Ni(2+), and Cr(3+)) and five anionic (Cl(-), NO3(-), SO4(2-), CrO4(2-), and Cr2O7(2-)) species was determined as a function of concentration in Franz diffusion cells. Cation transport numbers for four of these electrolytes were measured in Franz cells by the electromotive force method. Parallel experiments were conducted in solutions alone to establish the validity of the technique. Molar conductance decreased with increasing concentration, following the Kohlrausch law, over a 4-12-fold concentration range. Molar conductance and cation transport values at infinite dilution were extrapolated from these data and used to estimate ionic conductances at infinite dilution. These values were subsequently used to calculate limiting ion mobilities and diffusivities in solution and skin. Results for skin showed the expected increase in cation permselectivity for monovalent cations and a 40-110-fold reduction in effective diffusivities with respect to those in solution. However, Ni(2+) and Cr(3+) were relatively less mobile in skin than in solution. Salt diffusivities calculated from ionic mobilities in skin provided a partial explanation for the difference in allergenic potency of NiCl2 compared with NiSO4 and Cr(3+) versus Cr(6+) salts. PMID:23686652

  13. Cation-cation interactions, magnetic communication and reactivity of the pentavalent uraniumion [U(NR)2]+

    SciTech Connect

    Spencer, Liam P; Schelter, Eric J; Boncella, James M; Yang, Ping; Gsula, Robyn L; Scott, Brian L; Thompson, Joe D; Kiplinger, Jacqueline L; Batista, Enrique R

    2009-01-01

    The dimeric bis(imido) uranium complex [{l_brace}U(NtBu)2(I)(tBu2bpy){r_brace}2] (see picture; U green, N blue, I red) has cation-cation interactions between [U(NR)2]+ ions. This f1-f1 system also displays f orbital communication between uranium(V) centers at low temperatures, and can be oxidized to generate uranium(VI) bis(imido) complexes.

  14. Structural evolution of the methane cation in subfemtosecond photodynamics.

    PubMed

    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 CH4 (+) in subfemtosecond resolved photodynamics. The method utilizes time-dependent wave-packet propagation on the X˜(2)T2 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. PMID:26156480

  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. Crystal structure of the channelrhodopsin light-gated cation channel

    PubMed Central

    Kato, Hideaki E.; Zhang, Feng; Yizhar, Ofer; Ramakrishnan, Charu; Nishizawa, Tomohiro; Hirata, Kunio; Ito, Jumpei; Aita, Yusuke; Tsukazaki, Tomoya; Hayashi, Shigehiko; Hegemann, Peter; Maturana, Andrés D.; Ishitani, Ryuichiro; Deisseroth, Karl; Nureki, Osamu

    2014-01-01

    Channelrhodopsins (ChRs) are light-gated cation channels derived from algae that have shown experimental utility in optogenetics; for example, neurons expressing ChRs can be optically controlled with high temporal precision within systems as complex as freely moving mammals. Although ChRs have been broadly applied to neuroscience research, little is known about the molecular mechanisms by which these unusual and powerful proteins operate. Here we present the crystal structure of a ChR (a C1C2 chimaera between ChR1 and ChR2 from Chlamydomonas reinhardtii) at 2.3 Å resolution. The structure reveals the essential molecular architecture of ChRs, including the retinal-binding pocket and cation conduction pathway. This integration of structural and electrophysiological analyses provides insight into the molecular basis for the remarkable function of ChRs, and paves the way for the precise and principled design of ChR variants with novel properties. PMID:22266941

  17. Conducting a thermal conductivity survey

    NASA Technical Reports Server (NTRS)

    Allen, P. B.

    1985-01-01

    A physically transparent approximate theory of phonon decay rates is presented starting from a pair potential model of the interatomic forces in an insulator or semiconductor. The theory applies in the classical regime and relates the 3-phonon decay rate to the third derivative of the pair potential. Phonon dispersion relations do not need to be calculated, as sum rules relate all the needed quantities directly to the pair potential. The Brillouin zone averaged phonon lifetime turns out to involve a dimensionless measure of the anharmonicity multiplied by an effective density of states for 3-phonon decay. Results are given for rare gas and alkali halide crystals. For rare gases, the results are in good agreement with more elaborate perturbation calculations. Comparison to experimental data on phonon linewidths and thermal conductivity are made.

  18. Structural Isomerization of the Gas Phase 2-NORBORNYL Cation Revealed with Infrared Spectroscopy and Computational Chemistry

    NASA Astrophysics Data System (ADS)

    Mauney, Daniel; Mosley, Jonathan; Duncan, Michael A.

    2014-06-01

    The non-classical structure of the 2-norborny cation (C_7H11+) which was at the center of "the most heated chemical controversy of our time" has been observed in the condensed phase and recently using X-ray crystallography. However, no gas phase vibrational spectrum has been collected. The C_7H11+ cation is produced via H_3+ protonation of norbornene by pulsed discharge in a supersonic expansion of H_2/Ar. Ions are mass-selected and probed using infrared photodissociation spectroscopy. Due to high exothermicity, protonation via H_3+ leads to a structural isomerization to the global minimum structure 1,3-dimethylcyclopentenyl (DMCP+). Experiments are currently being conducted to find softer protonation techniques that could lead to the authentic 2-norbornyl cation. Schleyer,P.v.R. et. al.; Stable Carbocation Chemistry, John Wiley & Sons,Inc.; New York, 1997, Chapter 2

  19. Measuring the local electrical conductivity of human brain tissue

    NASA Astrophysics Data System (ADS)

    Akhtari, M.; Emin, D.; Ellingson, B. M.; Woodworth, D.; Frew, A.; Mathern, G. W.

    2016-02-01

    The electrical conductivities of freshly excised brain tissues from 24 patients were measured. The diffusion-MRI of the hydrogen nuclei of water molecules from regions that were subsequently excised was also measured. Analysis of these measurements indicates that differences between samples' conductivities are primarily due to differences of their densities of solvated sodium cations. Concomitantly, the sample-to-sample variations of their diffusion constants are relatively small. This finding suggests that non-invasive in-vivo measurements of brain tissues' local sodium-cation density can be utilized to estimate its local electrical conductivity.

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

    SciTech Connect

    Uberuaga, Blas Pedro; Pilania, Ghanshyam

    2015-07-08

    Perovskite structured oxides (ABO3) are attractive for a number of technological applications, including as superionics because of the high oxygen conductivities they exhibit. Double perovskites (AA’BB’O6) 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 SrLaTiAlO6. 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 end 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 Ti4+ 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.

  1. Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

    DOE PAGESBeta

    Kim, Michelle J.; Zoerb, Matthew C.; Campbell, Nicole R.; Zimmermann, Kathryn J.; Blomquist, Byron W.; Huebert, Barry J.; Bertram, Timothy H.

    2016-04-05

    Here, benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e., DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical-ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt−1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a much weaker electric field, demonstrated that ion–molecule reactions likely proceed through a combinationmore » of ligand-switching and direct charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (< 25 %) was observed for the detection of β-caryophyllene, a bicyclic sesquiterpene. The in-field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer, where measurements from the two instruments were highly correlated (R2 > 0.95, 10 s averages) over a wide range of sampling conditions.« less

  2. Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Kim, Michelle J.; Zoerb, Matthew C.; Campbell, Nicole R.; Zimmermann, Kathryn J.; Blomquist, Byron W.; Huebert, Barry J.; Bertram, Timothy H.

    2016-04-01

    Benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e., DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical-ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt-1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a much weaker electric field, demonstrated that ion-molecule reactions likely proceed through a combination of ligand-switching and direct charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (< 25 %) was observed for the detection of β-caryophyllene, a bicyclic sesquiterpene. The in-field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer, where measurements from the two instruments were highly correlated (R2 > 0.95, 10 s averages) over a wide range of sampling conditions.

  3. Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Kim, M. J.; Zoerb, M. C.; Campbell, N. R.; Zimmermann, K. J.; Blomquist, B. W.; Huebert, B. J.; Bertram, T. H.

    2015-10-01

    Benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e. DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt-1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a weaker electric field, demonstrated that ion-molecule reactions likely proceed through a combination of ligand-switching and direct charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (< 25 %) was observed for the detection of β-caryophyllene, a bicyclic sesquiterpene. The field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer. Measurements from the two instruments were highly correlated (R2=0.80) over a wide range of sampling conditions.

  4. Colloid Facilitated Transport of Radioactive Cations in the Vadose Zone: Field Experiments Oak Ridge

    SciTech Connect

    James E. Saiers

    2012-09-20

    The overarching goal of this study was to improve understanding of colloid-facilitated transport of radioactive cations through unsaturated soils and sediments. We conducted a suite of laboratory experiments and field experiments on the vadose-zone transport of colloids, organic matter, and associated contaminants of interest to the U.S. Department of Energy (DOE). The laboratory and field experiments, together with transport modeling, were designed to accomplish the following detailed objectives: 1. Evaluation of the relative importance of inorganic colloids and organic matter to the facilitation of radioactive cation transport in the vadose zone; 2. Assessment of the role of adsorption and desorption kinetics in the facilitated transport of radioactive cations in the vadose zone; 3. Examination of the effects of rainfall and infiltration dynamics and in the facilitated transport of radioactive cations through the vadose zone; 4. Exploration of the role of soil heterogeneity and preferential flow paths (e.g., macropores) on the facilitated transport of radioactive cations in the vadose zone; 5. Development of a mathematical model of facilitated transport of contaminants in the vadose zone that accurately incorporates pore-scale and column-scale processes with the practicality of predicting transport with readily available parameters.

  5. Penetrating cation/fatty acid anion pair as a mitochondria-targeted protonophore.

    PubMed

    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

    2010-01-12

    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 (C(12)TPP). 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 (DeltapH) to a membrane potential (Deltapsi) of the Nernstian value (about 60 mV Deltapsi at DeltapH = 1). A hydrophobic cation with localized charge (cetyltrimethylammonium) failed to substitute for hydrophobic cations with delocalized charge. In isolated mitochondria, SkQ1 and C(12)TPP, but not cetyltrimethylammonium, potentiated fatty acid-induced (i) uncoupling of respiration and phosphorylation, and (ii) inhibition of H(2)O(2) formation. In intact yeast cells, C(12)TPP 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. 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

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

    DOE PAGESBeta

    Uberuaga, Blas Pedro; Pilania, Ghanshyam

    2015-07-08

    Perovskite structured oxides (ABO3) are attractive for a number of technological applications, including as superionics because of the high oxygen conductivities they exhibit. Double perovskites (AA’BB’O6) 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 SrLaTiAlO6. 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 end member single perovskites.more » 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 Ti4+ 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

  8. Monovalent cation transport in irreversibly sickled cells.

    PubMed Central

    Clark, M R; Morrison, C E; Shohet, S B

    1978-01-01

    Using discontinuous density gradients of Stractan II, we have separated sickle cell blood into discrete subpopulations of reticulocytes, mature discoid cells, and irreversibly sickled cells (ISCs). We have measured active and passive fluxes of monovalent cations in mature discoid cells, ISCs, and normal control cells, also separated upon density gradients. These measurements revealed a decreased active cation transport in ISC-rich populations. However, parallel measurements of Na, K-ATPase activity showed normal ouabain-sensitive ATPase activity in ISCs. Passive permeability to external Rb was also normal in ISCs. The observation of depressed pump activity in intact ISCs, contrasted with normal ATPase activity in ISC membranes, suggests the presence of factors in the intact cell which inhibit the active transport of Na and K in ISCs. PMID:149799

  9. Cation specific binding with protein surface charges.

    PubMed

    Hess, Berk; van der Vegt, Nico F A

    2009-08-11

    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

  10. Electronic spectrum of 9-methylanthracenium radical cation

    NASA Astrophysics Data System (ADS)

    O'Connor, Gerard D.; Sanelli, Julian A.; Dryza, Vik; Bieske, Evan J.; Schmidt, Timothy W.

    2016-04-01

    The predissociation spectrum of the cold, argon-tagged, 9-methylanthracenium radical cation is reported from 8000 cm-1 to 44 500 cm-1. The reported spectrum contains bands corresponding to at least eight electronic transitions ranging from the near infrared to the ultraviolet. These electronic transitions are assigned through comparison with ab initio energies and intensities. The infrared D1←D0 transitions exhibit significant vibronic activity, which is assigned through comparison with TD-B3LYP excited state frequencies and intensities, as well as modelled vibronic interactions. Dissociation of 9-methylanthracenium is also observed at high visible-photon energies, resulting in the loss of either CH2 or CH3. The relevance of these spectra, and the spectra of other polycyclic aromatic hydrocarbon radical cations, to the largely unassigned diffuse interstellar bands, is discussed.

  11. [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.

  12. Ultrafast dynamics of water in cationic micelles

    NASA Astrophysics Data System (ADS)

    Dokter, Adriaan M.; Woutersen, Sander; Bakker, Huib J.

    2007-03-01

    The effect of confinement on the dynamical properties of liquid water is investigated for water enclosed in cationic reverse micelles. The authors performed mid-infrared ultrafast pump-probe spectroscopy on the OH-stretch vibration of isotopically diluted HDO in D2O in cetyltrimethylammonium bromide (CTAB) reverse micelles of various sizes. The authors observe that the surfactant counterions are inhomogeneously distributed throughout the reverse micelle, and that regions of extreme salinity occur near the interfacial Stern layer. The authors find that the water molecules in the core of the micelles show similar orientational dynamics as bulk water, and that water molecules in the counterion-rich interfacial region are much less mobile. An explicit comparison is made with the dynamics of water confined in anionic sodium bis(2-ethythexyl) sulfosuccinate (AOT) reverse micelles. The authors find that interfacial water in cationic CTAB reverse micelles has a higher orientational mobility than water in anionic AOT reverse micelles.

  13. Plant NHX cation/proton antiporters

    PubMed Central

    Rodríguez-Rosales, M Pilar; Gálvez, Francisco J; Huertas, Raúl; Aranda, M Nieves; Baghour, Mourad; Cagnac, Olivier

    2009-01-01

    Although physiological and biochemical data since long suggested that Na+/H+ and K+/H+ antiporters are involved in intracellular ion and pH regulation in plants, it has taken a long time to identify genes encoding antiporters that could fulfil these roles. Genome sequencing projects have now shown that plants contain a very large number of putative Cation/Proton antiporters, the function of which is only beginning to be studied. The intracellular NHX transporters constitute the first Cation/Proton exchanger family studied in plants. The founding member, AtNHX1, was identified as an important salt tolerance determinant and suggested to catalyze Na+ accumulation in vacuoles. It is, however, becoming increasingly clear, that this gene and other members of the family also play crucial roles in pH regulation and K+ homeostasis, regulating processes from vesicle trafficking and cell expansion to plant development. PMID:19794841

  14. Alkaline earth cation extraction from acid solution

    DOEpatents

    Dietz, Mark; Horwitz, E. Philip

    2003-01-01

    An extractant medium for extracting alkaline earth cations from an aqueous acidic sample solution is described as are a method and apparatus for using the same. The separation medium is free of diluent, free-flowing and particulate, and comprises a Crown ether that is a 4,4'(5')[C.sub.4 -C.sub.8 -alkylcyclohexano]18-Crown-6 dispersed on an inert substrate material.

  15. Regulation of Cation Balance in Saccharomyces cerevisiae

    PubMed Central

    Cyert, Martha S.; Philpott, Caroline C.

    2013-01-01

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

  16. 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

  17. Insights into the transport of aqueous quaternary ammonium cations: a combined experimental and computational study.

    PubMed

    Sarode, Himanshu N; Lindberg, Gerrick E; Yang, Yuan; Felberg, Lisa E; Voth, Gregory A; Herring, Andrew M

    2014-02-01

    This study focuses on understanding the relative effects of ammonium substituent groups (we primarily consider tetramethylammonium, benzyltrimethylammonium, and tetraethylammonium cations) and anion species (OH(-), HCO3(-), CO3(2-), Cl(-), and F(-)) on ion transport by combining experimental and computational approaches. We characterize transport experimentally using ionic conductivity and self-diffusion coefficients measured from NMR. These experimental results are interpreted using simulation methods to describe the transport of these cations and anions considering the effects of the counterion. It is particularly noteworthy that we directly probe cation and anion diffusion with pulsed gradient stimulated echo NMR and molecular dynamics simulations, corroborating these methods and providing a direct link between atomic-resolution simulations and macroscale experiments. By pairing diffusion measurements and simulations with residence times, we were able to understand the interplay between short-time and long-time dynamics with ionic conductivity. With experiment, we determined that solutions of benzyltrimethylammonium hydroxide have the highest ionic conductivity (0.26 S/cm at 65 °C), which appears to be due to differences for the ions in long-time diffusion and short-time water caging. We also examined the effect of CO2 on ionic conductivity in ammonium hydroxide solutions. CO2 readily reacts with OH(-) to form HCO(-)3 and is found to lower the solution ionic conductivity by almost 50%. PMID:24437699

  18. Low cation coordination in oxide melts

    SciTech Connect

    Skinner, Lawrie; Benmore, Chris J; Du, Jincheng; Weber, Richard; Neuefeind, Joerg C; Tumber, Sonia; Parise, John B

    2014-01-01

    The complete set of Faber-Ziman partial pair distribution functions for a rare earth oxide liquid were measured for the first time by combining aerodynamic levitation, neutron diffraction, high energy x-ray diffraction and isomorphic substitution using Y2 O3 and Ho2 O3 melts. The average Y- O coordination is measured to be 5.5(2), which is significantly less than the octahedral coordination of crystalline Y2 O3 (or Ho2 O3 ). Investigation of high temperature La2 O3 , ZrO2 , SiO2 , and Al2 O3 melts by x-ray diffraction and molecular dynamics simulations also show lower-than-crystal cation- oxygen coordination. These measurements suggest a general trend towards lower M-O coordination compared to their crystalline counterparts. It is found that this coordination number drop is larger for lower field strength, larger radius cations and is negligible for high field strength (network forming) cations. These findings have broad implications for predicting the local structure and related physical properties of metal-oxide melts and oxide glasses.

  19. Reducible cationic lipids for gene transfer.

    PubMed Central

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

    2001-01-01

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

  20. Study of the fluoro- and chlorodimethylbutyl cations

    PubMed Central

    Olah, George A.; Prakash, G. K. Surya; Rasul, Golam

    2013-01-01

    A comparative study of the 2,3-dimethyl-3-fluoro-2-butyl cation and its chloro analog was carried out by the ab initio/GIAO-CCSD(T) (gauge invariant atomic orbital-coupled cluster with single, double, and perturbative triple excitation) method. The structures and 13C NMR chemical shifts of the cations were calculated at the GIAO-CCSD(T)/tzp/dz//MP2/cc-pVTZ level. Bridged fluoronium ion 1, carbenium ion 2, and fluorocarbenium ion 3 were found to be minima on the potential energy surface. Bridged fluoronium ion 1, although a minimum on the potential energy surface, is 12.8 kcal/mol less stable than the open chain fluorobutyl cation 3. In contrast to the fluorinated ion, bridged chloronium ion 5 was found to be the lowest energy minimum being 10.6 kcal/mol more stable than ion 6 and 7.4 kcal/mol more stable than ion 7. PMID:23650369

  1. Modulation of mechanosensitive calcium-selective cation channels by temperature

    NASA Technical Reports Server (NTRS)

    Ding, J. P.; Pickard, B. G.

    1993-01-01

    Gating of associations of mechanosensitive Ca(2+)-selective cation co-channels in the plasmalemma of onion epidermis has a strong and unusual temperature dependence. Tension-dependent activity rises steeply as temperature is lowered from 25 degrees C to about 6 degrees C, but drops to a low level at about 5 degrees C. Under the conditions tested (with Mg2+ and K+ at the cytosolic face of outside-out membrane patches), promotion results both from more bursting at all observed linkage levels and from longer duration of bursts of co-channels linked as quadruplets and quintuplets. Co-channel conductance decreases linearly, but only modestly, with declining temperature. It is proposed that these and related mechanosensitive channels may participate in a variety of responses to temperature, including thermonasty, thermotropism, hydrotropism, and both cold damage and cold acclimation.

  2. Cationic isotachophoresis separation of the biomarker cardiac troponin I from a high-abundance contaminant, serum albumin

    PubMed Central

    Jacroux, Thomas; Bottenus, Danny; Rieck, Bennett; Ivory, Cornelius F.; Dong, Wen-ji

    2014-01-01

    Cationic ITP was used to separate and concentrate fluorescently tagged cardiac troponin I (cTnI) from two proteins with similar isoelectric properties in a PMMA straight-channel microfluidic chip. In an initial set of experiments, cTnI was effectively separated from R-Phycoerythrin using cationic ITP in a pH 8 buffer system. Then, a second set of experiments was conducted in which cTnI was separated from a serum contaminant, albumin. Each experiment took ~ 10 min or less at low electric field strengths (34 V/cm) and demonstrated that cationic ITP could be used as an on-chip removal technique to isolate cTnI from albumin. In addition to the experimental work, a 1D numerical simulation of our cationic ITP experiments has been included to qualitatively validate experimental observations. PMID:24723384

  3. Cationic isotachophoresis separation of the biomarker cardiac troponin I from a high-abundance contaminant, serum albumin.

    PubMed

    Jacroux, Thomas; Bottenus, Danny; Rieck, Bennett; Ivory, Cornelius F; Dong, Wen-Ji

    2014-07-01

    Cationic ITP was used to separate and concentrate fluorescently tagged cardiac troponin I (cTnI) from two proteins with similar isoelectric properties in a PMMA straight-channel microfluidic chip. In an initial set of experiments, cTnI was effectively separated from R-Phycoerythrin using cationic ITP in a pH 8 buffer system. Then, a second set of experiments was conducted in which cTnI was separated from a serum contaminant, albumin. Each experiment took ∼10 min or less at low electric field strengths (34 V/cm) and demonstrated that cationic ITP could be used as an on-chip removal technique to isolate cTnI from albumin. In addition to the experimental work, a 1D numerical simulation of our cationic ITP experiments has been included to qualitatively validate experimental observations. PMID:24723384

  4. Cationic and anionic environments in LiTFSI-doped di-ureasils with application in solid-state electrochromic devices

    NASA Astrophysics Data System (ADS)

    Nunes, S. C.; de Zea Bermudez, V.; Ostrovskii, D.; Barbosa, P. C.; Silva, M. M.; Smith, M. J.

    2008-04-01

    Fourier Transform mid-infrared and Raman spectroscopies were used to investigate the cation/polymer, cation/urea bridge, cation/anion and hydrogen bonding interactions in poly(oxyethylene) (POE)/siloxane di-ureasil networks prepared by the sol-gel route and doped with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). Materials with compositions 200 ⩾ n ⩾ 5 (where n expresses the molar ratio OCH 2CH 2/Li +) were studied. The Li + ions coordinate to the urea carbonyl oxygen atoms over the whole range of salt concentration considered. Bonding to the ether oxygen atoms of the POE chains occurs at n ⩽ 40, although a significant fraction of the POE chains remain non-coordinated. In these high salt content samples, the cations interact with the anions forming contact ion pairs. "Free" ions are probably the main charge carriers at the room temperature conductivity maximum of these ormolytes.

  5. Cation uptake and allocation by red pine seedlings under cation-nutrient stress in a column growth experiment

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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 stress on cation uptake in an experimental plant-mineral system. Methods: Column experim...

  6. Dependence of spontaneous electrical activity and basal prolactin release on nonselective cation channels in pituitary lactotrophs.

    PubMed

    Kučka, M; Kretschmannová, K; Stojilkovic, S S; Zemková, H; Tomić, M

    2012-01-01

    All secretory anterior pituitary cells fire action potentials spontaneously and exhibit a high resting cation conductance, but the channels involved in the background permeability have not been identified. In cultured lactotrophs and immortalized GH(3) cells, replacement of extracellular Na(+) with large organic cations, but not blockade of voltage-gated Na(+) influx, led to an instantaneous hyperpolarization of cell membranes that was associated with a cessation of spontaneous firing. When cells were clamped at -50 mV, which was close to the resting membrane potential in these cells, replacement of bath Na(+) with organic cations resulted in an outward-like current, reflecting an inhibition of the inward holding membrane current and indicating loss of a background-depolarizing conductance. Quantitative RT-PCR analysis revealed the high expression of mRNA transcripts for TRPC1 and much lower expression of TRPC6 in both lactotrophs and GH(3) cells. Very low expression of TRPC3, TRPC4, and TRPC5 mRNA transcripts were also present in pituitary but not GH(3) cells. 2-APB and SKF-96365, relatively selective blockers of TRPC channels, inhibited electrical activity, Ca(2+) influx and prolactin release in a concentration-dependent manner. Gd(3+), a common Ca(2+) channel blocker, and flufenamic acid, an inhibitor of non-selective cation channels, also inhibited electrical activity, Ca(2+) influx and prolactin release. These results indicate that nonselective cation channels, presumably belonging to the TRPC family, contribute to the background depolarizing conductance and firing of action potentials with consequent contribution to Ca(2+) influx and hormone release in lactotrophs and GH(3) cells. PMID:22480423

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

    SciTech Connect

    Ye, Chuyu; Yang, Xiaohan; Xia, Xinli; Yin, Weilun

    2013-01-01

    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 specieswas reported.We identified 240 cation/proton antiporters in alga, moss, and angiosperm. A phylogenetic tree was constructed showing these 240members 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 angiospermspecies. Sliding windowanalysis 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 foundmostmotifs 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.

  8. Radiolytic generation of radical cations in xenon matrices. Tetramethylcyclopropane radical cation and its transformations

    SciTech Connect

    Qin, X.Z.; Trifunac, A.D. )

    1990-04-05

    Radiolytic generation of radical cations in xenon matrices containing electron scavengers is illustrated by studying the 1,1,2,2-tetramethylcyclopropane radical cation. Dilute and concentrated solutions of tetramethylcyclopropane in xenon without electron scavengers and neat tetramethylcyclopropane yielded neutral radicals upon {gamma}-irradiation. Speculation on the mechanisms of radical formation is presented. The radical species observed in the {gamma}-irradiation of neat tetramethylcyclopropane appears to be identical with the paramagnetic species observed in CF{sub 2}ClCFCl{sub 2} above 120 K, suggesting that a neutral radical rather than the ring-opened distonic radical cation is observed in the CF{sub 2}ClCFCl{sub 2} matrix.

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

    SciTech Connect

    Balboni, Enrica; Burns, Peter C.

    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 a 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 hydrothermal

  10. Ultrafast dynamics of pyrrolidinium cation ionic liquids.

    PubMed

    Shirota, Hideaki; Funston, Alison M; Wishart, James F; Castner, Edward W

    2005-05-01

    We have investigated the ultrafast molecular dynamics of five pyrrolidinium cation room temperature ionic liquids using femtosecond optical heterodyne-detected Raman-induced Kerr effect spectroscopy. The ionic liquids studied are N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P14+/NTf2-), N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P1EOE+/NTf2-), N-ethoxyethyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P1EOE+/NTf2-), N-ethoxyethyl-N-methylpyrrolidinium bromide P1EOE+, and N-ethoxyethyl-N-methylpyrrolidinium dicyanoamide P1EOE+/DCA-). For comparing dynamics among the five ionic liquids, we categorize the ionic liquids into two groups. One group of liquids comprises the three pyrrolidinium cations P14+, P1EOM+, and P1EOE+ paired with the NTf2- anion. The other group of liquids consists of the P1EOE+ cation paired with each of the three anions NTf2-, Br-, and DCA-. The overdamped relaxation for time scales longer than 2 ps has been fit by a triexponential function for each of the five pyrrolidinium ionic liquids. The fast ( approximately 2 ps) and intermediate (approximately 20 ps) relaxation time constants vary little among these five ionic liquids. However, the slow relaxation time constant correlates with the viscosity. Thus, the Kerr spectra in the range from 0 to 750 cm(-1) are quite similar for the group of three pyrrolidinium ionic liquids paired with the NTf2- anion. The intermolecular vibrational line shapes between 0 and 150 cm(-1) are fit to a multimode Brownian oscillator model; adequate fits required at least three modes to be included in the line shape. PMID:15918734

  11. Ultrafast dynamics of pyrrolidinium cation ionic liquids

    NASA Astrophysics Data System (ADS)

    Shirota, Hideaki; Funston, Alison M.; Wishart, James F.; Castner, Edward W.

    2005-05-01

    We have investigated the ultrafast molecular dynamics of five pyrrolidinium cation room temperature ionic liquids using femtosecond optical heterodyne-detected Raman-induced Kerr effect spectroscopy. The ionic liquids studied are N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P14+/NTf2-), N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P1EOE+/NTf2-), N-ethoxyethyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P1EOE+/NTf2-), N-ethoxyethyl-N-methylpyrrolidinium bromideP1EOE+, and N-ethoxyethyl-N-methylpyrrolidinium dicyanoamide P1EOE+/DCA-). For comparing dynamics among the five ionic liquids, we categorize the ionic liquids into two groups. One group of liquids comprises the three pyrrolidinium cations P14+, P1EOM+, and P1EOE+ paired with the NTf2- anion. The other group of liquids consists of the P1EOE+ cation paired with each of the three anions NTf2-,Br-, and DCA-. The overdamped relaxation for time scales longer than 2 ps has been fit by a triexponential function for each of the five pyrrolidinium ionic liquids. The fast (˜2ps) and intermediate (˜20ps) relaxation time constants vary little among these five ionic liquids. However, the slow relaxation time constant correlates with the viscosity. Thus, the Kerr spectra in the range from 0 to 750cm-1 are quite similar for the group of three pyrrolidinium ionic liquids paired with the NTf2- anion. The intermolecular vibrational line shapes between 0 and 150cm-1 are fit to a multimode Brownian oscillator model; adequate fits required at least three modes to be included in the line shape.

  12. Cationic bituminous emulsions and emulsion aggregate slurries

    SciTech Connect

    Schilling, P.

    1986-07-01

    A cationic bituminous emulsion is described which consists of from about 30% to about 80% by weight of bitumen, from about 0.1% to about 10% by weight of an emulsifier selected from the group consisting of reaction products of a polyamine reacted with a member of the group consisting of epoxidized unsaturated fatty acids of chain lengths between C/sub 8/ and C/sub 22/ and the esters thereof and adding water to make up 100% by weight, the emulsion having a pH in the range of from 2-7.

  13. Nonclassical 21-Homododecahedryl Cation Rearrangement Revisited.

    PubMed

    Jalife, Said; Mondal, Sukanta; Osorio, Edison; Cabellos, José Luis; Martínez-Guajardo, Gerardo; Fernández-Herrera, María A; Merino, Gabriel

    2016-03-01

    The degenerate rearrangement in the 21-homododecahedryl cation (1) has been studied via density functional theory computations and Born-Oppenheimer Molecular Dynamics simulations. Compound 1 can be described as a highly fluxional hyperconjugated carbocation. Complete scrambling of 1 can be achieved by the combination of two unveiled barrierless processes. The first one is a "rotation" of one of the six-membered rings via a 0.8 kcal·mol(-1) barrier, and the second one is a slower interconvertion between two hyperconjomers via an out-of-plane methine bending (ΔG(⧧) = 4.0 kcal·mol(-1)). PMID:26862680

  14. Mobility of cations in magnesium aluminate spinel

    NASA Astrophysics Data System (ADS)

    Martinelli, J. R.; Sonder, E.; Weeks, R. A.; Zuhr, R. A.

    1986-04-01

    Transport of cations in magnesium aluminate spinel due to an applied electric field at approximately 1000 °C has been measured by observing changes in elemental concentrations near the cathode and anode surfaces using ion backscattering techniques. The results indicate that magnesium ions are the mobile species at 1000 °C and that these ions combine with ambient oxygen at the cathode surface to form a MgO layer. Quantitative interpretation of the data leads to the conclusion that the ionic transference number of spinel becomes approximately 0.5 after treatment in an electric field.

  15. Fragmentation Pathways in the Uracil Radical Cation

    SciTech Connect

    Zhou, Congyi; Matsika, Spiridoula; Kotur, Marija; Weinacht, Thomas C.

    2012-08-24

    We investigate pathways for fragmentation in the uracil radical cation using ab initio electronic structure calculations. We focus on the main fragments produced in pump–probe dissociative ionization experiments. These are fragments with mass to charge ratios (m/z) of 69, 28, 41, and 42. Barriers to dissociation along the ground ionic surface are reported, which provide an estimate of the energetic requirements for the production of the main fragments. Finally, direct and sequential fragmentation mechanisms have been analyzed, and it is concluded that sequential fragmentation after production of fragment with m/z 69 is the dominant mechanism for the production of the smaller fragments.

  16. Soil Cation Status in Southern California: Interactions of Vehicular Emissions

    NASA Astrophysics Data System (ADS)

    Rossi, R.; Bain, D. J.; Jenerette, D.; Clarke, L. W.

    2012-12-01

    Roadside soils are often enriched in trace metals due to vehicular deposition. However, less attention is given to base cation pools in roadside soils. Relatively high loadings of nitrate from vehicular exhaust should acidify roadside soils, potentially mobilizing cationic species by displacing them from soil exchange sites. In contrast, weathering of road materials can contribute substantial amounts of these cations to the same soils, potentially replenishing cation pools. Base cations are essential nutrients and these dynamics may alter ecosystem processes in near-road environments. Metal concentrations in park and garden soils collected from Southern California (Los Angeles and Riverside Counties) were examined across gradients of road network intensity, climate and geology. In these samples, base cation concentrations decrease in areas of denser road networks. Base cation concentrations also decrease with distance from the road, with near-road samples relatively depleted in base cation concentrations. In addition, base cation concentrations are associated with traffic flux density, with exchange pools decreasing near heavily trafficked areas. These relationships suggest road activity is mobilizing cations, depleting near-road soils of essential nutrient pools, despite road material weathering. This depletion of soil nutrients from exchange pools in roadside soils likely influences local ecological function in unpredictable ways. This observation lays the groundwork for continued characterization of soil metal processes in the increasingly common roadside environment.

  17. Evaluation of cation-anion interaction strength in ionic liquids.

    PubMed

    Fernandes, Ana M; Rocha, Marisa A A; Freire, Mara G; Marrucho, Isabel M; Coutinho, João A P; Santos, Luís M N B F

    2011-04-14

    Electrospray ionization mass spectrometry with variable collision induced dissociation of the isolated [(cation)(2)anion](+) and/or [(anion)(2)cation](-) ions of imidazolium-, pyridinium-, pyrrolidinium-, and piperidinium-based ionic liquids (ILs) combined with a large set of anions, such as chloride, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, and bis[(trifluoromethyl)sulfonyl]imide, was used to carry out a systematic and comprehensive study on the ionic liquids relative interaction energies. The results are interpreted in terms of main influences derived from the structural characteristics of both anion and cation. On the basis of quantum chemical calculations, the effect of the anion upon the dissociation energies of the ionic liquid pair, and isolated [(cation)(2)anion](+) and/or [(anion)(2)cation](-) aggregates, were estimated and are in good agreement with the experimental data. Both experimental and computational results indicate an energetic differentiation between the cation and the anion to the ionic pair. Moreover, it was found that the quantum chemical calculations can describe the trend obtained for the electrostatic cation-anion attraction potential. The impact of the cation-anion interaction strengths in the surface tension of ionic liquids is further discussed. The surface tensions dependence on the cation alkyl chain length, and on the anion nature, follows an analogous pattern to that of the relative cation-anion interaction energies determined by mass spectrometry. PMID:21425809

  18. Mechanically driven activation of polyaniline into its conductive form.

    PubMed

    Baytekin, Bilge; Baytekin, H Tarik; Grzybowski, Bartosz A

    2014-07-01

    Mechanical treatment of polymers produces surface cations and anions which, as demonstrated here for the first time, can drive chemical reactions. In particular, it is shown that such a mechanical treatment transforms nonconductive polyaniline into its conductive form. These results provide a mechanical means of patterning conductive polymers and also coating small polymer objects with conductive polyaniline films preventing accumulation of static electricity. PMID:24824971

  19. 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

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

    PubMed

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

    2016-06-01

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

  1. Photodissociation of Cerium Oxide Nanocluster Cations.

    PubMed

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

    2016-04-21

    Cerium oxide cluster cations, CexOy(+), are produced via laser vaporization in a pulsed nozzle source and detected with time-of-flight mass spectrometry. The mass spectrum displays a strongly preferred oxide stoichiometry for each cluster with a specific number of metal atoms x, with x ≤ y. Specifically, the most prominent clusters correspond to the formula CeO(CeO2)n(+). The cluster cations are mass selected and photodissociated with a Nd:YAG laser at either 532 or 355 nm. The prominent clusters dissociate to produce smaller species also having a similar CeO(CeO2)n(+) formula, always with apparent leaving groups of (CeO2). The production of CeO(CeO2)n(+) from the dissociation of many cluster sizes establishes the relative stability of these clusters. Furthermore, the consistent loss of neutral CeO2 shows that the smallest neutral clusters adopt the same oxidation state (IV) as the most common form of bulk cerium oxide. Clusters with higher oxygen content than the CeO(CeO2)n(+) masses are present with much lower abundance. These species dissociate by the loss of O2, leaving surviving clusters with the CeO(CeO2)n(+) formula. Density functional theory calculations on these clusters suggest structures composed of stable CeO(CeO2)n(+) cores with excess oxygen bound to the surface as a superoxide unit (O2(-)). PMID:27035210

  2. Nanoheterostructure Cation Exchange: Anionic Framework Conservation

    SciTech Connect

    Jain, Prashant K.; Amirav, Lilac; Aloni, Shaul; Alivisatos, A. Paul

    2010-05-11

    In ionic nanocrystals the cationic sub-lattice can be replaced with a different metal ion via a fast, simple, and reversible place-exchange, allowing post-synthetic modification of the composition of the nanocrystal, while preserving its size and shape. Here, we demonstrate for the first time that during such an exchange, the anionic framework of the crystal is preserved. When applied to nanoheterostructures, this phenomenon ensures that compositional interfaces within the heterostructure are conserved throughout the transformation. For instance, a morphology composed of a CdSe nanocrystal embedded in a CdS rod (CdSe/CdS) was exchanged to a PbSe/PbS nanorod via a Cu2Se/Cu2S structure. During every exchange cycle, the seed size and position within the nanorod were preserved, as evident by excitonic features, Z-contrast imaging, and elemental line-scans. Anionic framework conservation extends the domain of cation exchange to the design of more complex and unique nanostructures.

  3. Antibacterial Activity of Geminized Amphiphilic Cationic Homopolymers.

    PubMed

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

    2015-12-22

    The current study is aimed at investigating the effect of cationic charge density and hydrophobicity on the antibacterial and hemolytic activities. Two kinds of cationic surfmers, containing single or double hydrophobic tails (octyl chains or benzyl groups), and the corresponding homopolymers were synthesized. The antimicrobial activity of these candidate antibacterials was studied by microbial growth inhibition assays against Escherichia coli, and hemolysis activity was carried out using human red blood cells. It was interestingly found that the homopolymers were much more effective in antibacterial property than their corresponding monomers. Furthermore, the geminized homopolymers had significantly higher antibacterial activity than that of their counterparts but with single amphiphilic side chains in each repeated unit. Geminized homopolymers, with high positive charge density and moderate hydrophobicity (such as benzyl groups), combine both advantages of efficient antibacterial property and prominently high selectivity. To further explain the antibacterial performance of the novel polymer series, the molecular interaction mechanism is proposed according to experimental data which shows that these specimens are likely to kill microbes by disrupting bacterial membranes, leading them unlikely to induce resistance. PMID:26606647

  4. Divalent cation affinity sites in Paramecium aurelia.

    PubMed

    Fisher, G; Kaneshiro, E S; Peters, P D

    1976-05-01

    Sites with high calcium affinity in Paramecium aurelia were identified by high calcium (5 mM) fixation and electron microscope methods. Electron-opaque deposits were observed on the cytoplasmic side of surface membranes, particularly at the basal regions of cilia and trichocyst-pellicle fusion sites. Deposits were also observed on some smooth cytomembranes, within the axoneme of cilia, and on basal bodies. The divalent cations, Mg2+, Mn2+, Sr2+, Ni2+, Ba2+, and Zn2+, could be substituted for Ca2+ in the procedure. Deposits were larger with 5 mM Sr2+. Ba2+, and Mn2+ at ciliary transverse plates and the terminal plate of basal bodies. Microprobe analysis showed that Ca and C1 were concentrated within deposits. In some analyses, S and P were detected in deposits. Also, microprobe analysis of 5 mM Mn2+-fixed P. aurelia showed that those deposits were enriched in Mn and C1 and sometimes enriched in P. Deposits were seen only when the ciliates were actively swimming at the time of fixation. Locomotory mutants having defective membrane Ca-gating mechanisms and ciliates fixed while exhibiting ciliary reversal showed no obvious differences in deposition pattern and intensity. Possible correlations between electron-opaque deposits and the locations of intramembranous particles seen by freeze-fracture studied, as well as sites where fibrillar material associate with membranes are considered. The possibility that the action sites of calcium and other divalent cations were identified is discussed. PMID:1262398

  5. Cationic Antimicrobial Polymers and Their Assemblies

    PubMed Central

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

    2013-01-01

    Cationic compounds are promising candidates for development of antimicrobial agents. Positive charges attached to surfaces, particles, polymers, peptides or bilayers have been used as antimicrobial agents by themselves or in sophisticated formulations. The main positively charged moieties in these natural or synthetic structures are quaternary ammonium groups, resulting in quaternary ammonium compounds (QACs). The advantage of amphiphilic cationic polymers when compared to small amphiphilic molecules is their enhanced microbicidal activity. Besides, many of these polymeric structures also show low toxicity to human cells; a major requirement for biomedical applications. Determination of the specific elements in polymers, which affect their antimicrobial activity, has been previously difficult due to broad molecular weight distributions and random sequences characteristic of radical polymerization. With the advances in polymerization control, selection of well defined polymers and structures are allowing greater insight into their structure-antimicrobial activity relationship. On the other hand, antimicrobial polymers grafted or self-assembled to inert or non inert vehicles can yield hybrid antimicrobial nanostructures or films, which can act as antimicrobials by themselves or deliver bioactive molecules for a variety of applications, such as wound dressing, photodynamic antimicrobial therapy, food packing and preservation and antifouling applications. PMID:23665898

  6. Ceramic Spheres From Cation Exchange Beads

    NASA Technical Reports Server (NTRS)

    Dynys, F. W.

    2003-01-01

    Porous ZrO2 and hollow TiO2 spheres were synthesized from a strong acid cation exchange resin. Spherical cation exchange beads, polystyrene based polymer, were used as a morphological-directing template. Aqueous ion exchange reaction was used to chemically bind (ZrO)(2+) ions to the polystyrene structure. The pyrolysis of the polystyrene at 600 C produces porous ZrO2 spheres with a surface area of 24 sq m/g with a mean sphere size of 42 microns. Hollow TiO2 spheres were synthesized by using the beads as a micro-reactor. A direct surface reaction - between titanium isopropoxide and the resin beads forms a hydrous TiO2 shell around the polystyrene core. The pyrolysis of the polystyrene core at 600 C produces hollow anatase spheres with a surface area of 42 sq m/g with a mean sphere size of 38 microns. The formation of ceramic spheres was studied by XRD, SEM and B.E.T. nitrogen adsorption measurements.

  7. Interaction of Hyaluronan with Cationic Nanoparticles.

    PubMed

    Bano, Fouzia; Carril, Mónica; Di Gianvincenzo, Paolo; Richter, Ralf P

    2015-08-01

    The polysaccharide hyaluronan (HA) is a main component of peri- and extracellular matrix, and an attractive molecule for materials design in tissue engineering and nanomedicine. Here, we study the morphology of complexes that form upon interaction of nanometer-sized amine-coated gold particles with this anionic, linear, and regular biopolymer in solution and grafted to a surface. We find that cationic nanoparticles (NPs) have profound effects on HA morphology on the molecular and supramolecular scale. Quartz crystal microbalance (QCM-D) shows that depending on their relative abundance, cationic NPs promote either strong compaction or swelling of films of surface-grafted HA polymers (HA brushes). Transmission electron and atomic force microscopy reveal that the NPs do also give rise to complexes of distinct morphologies-compact nanoscopic spheres and extended microscopic fibers-upon interaction with HA polymers in solution. In particular, stable and hydrated spherical complexes of single HA polymers with NPs can be prepared when balancing the ionizable groups on HA and NPs. The observed self-assembly phenomena could be useful for the design of drug delivery vehicles and a better understanding of the reorganization of HA-rich synthetic or biological matrices. PMID:26146006

  8. Diffusion of highly charged cations in olivine

    NASA Astrophysics Data System (ADS)

    Cherniak, D. J.; Watson, E. B.; Liang, Y.

    2012-12-01

    Diffusion of tungsten, titanium and phosphorus have been measured in natural iron-bearing olivine (~Fo90) and synthetic forsterite. Experiments were run under buffered conditions (with iron-wustite or Ni-NiO buffers) in 1-atm furnaces. The sources of diffusant for experiments were MgWO4 for tungsten diffusion, Mg2TiO4 for Ti diffusion, and AlPO4 for P diffusion; in all cases these compounds were pre-reacted at high temperature with Mg2SiO4 or Fe-bearing olivine prior to diffusion anneals. Samples were placed with the source materials in noble metal or silica capsules, which were sealed under vacuum in silica glass ampoules with solid buffers. Rutherford backscattering spectrometry (RBS) was used to measure depth profiles for all sets of experiments; measurements of P were also made with Nuclear Reaction Analysis using the 31P(α,p)34S reaction. These new data suggest marked differences among diffusivities of these cations, with titanium diffusion faster than diffusion of tungsten, but slower than diffusion of phosphorus over the conditions investigated. Diffusivities of all of these elements appear significantly slower than those of divalent cations in olivine. These results will be discussed in context with extant diffusion data for major, trace and minor elements in olivine. The effects of oxygen fugacity and olivine composition on diffusion, and potential implications for diffusion mechanisms will also be considered.

  9. Resistivity Effects of Cation Ordering in Highly-Doped La2-xSrxCu4 Epitaxial Thin Films

    NASA Astrophysics Data System (ADS)

    Burquest, Franklin; Marmol, Rodrigo; Cox, Nicholas; Nelson-Cheeseman, Brittany

    Highly-doped La2-xSrxCuO4 (LSCO) films (0.5 <= x <= 1.0) are promising for many applications due to their electronic, ionic, and phonon transport. In this study, we investigate the effect of ``electrostatic strain'' on the electrical transport of LSCO thin films with large doping (x =0.5, 0.75, and 1.0). This ``electrostatic strain'' is applied by ordering differently charged A-site cations (La3+ vs. Sr2+) into charged A-O layers within the crystal structure. This causes internal polar electrostatic forces, which have been shown to cause stretching of the apical oxygen bond in analogous epitaxial nickelate films. Thin film samples are grown concurrently to minimize extraneous effects on film structure and properties. Atomic force microscopy and x-ray reflectivity demonstrate that the films are single crystalline, epitaxial, and smooth. X-ray diffraction is used to measure the c-axis of the films as a function of doping and dopant cation ordering. Electrical transport data of the ordered samples is compared with transport data of conventional disordered cation samples. Preliminary data indicates significant differences in resistivity at both 300K and 10K between the cation-ordered and cation-disordered samples. This work indicates that dopant cation ordering within the layered cuprates could significantly modify the conduction mechanisms at play in these materials.

  10. Log-derived cation exchange capacity of shaly sands: Application to hydrocarbon detection and drilling optimization

    NASA Astrophysics Data System (ADS)

    Ipek, Gamze

    Researchers at Louisiana State University, LSU, have introduced several petrophysical models expressing the electric properties of shaly sands. These models, to be used for hydrocarbon detection, are based on the Waxman and Smits concept of supplementing the water conductivity with a clay counterions conductivity. The LSU models also utilize the Dual Water theory, which relates each conductivity term to a particular type of water, free and bound, each occupying a specific volume of the total pore space. The main difference between these models and the other shaly sand models is that the counterion conductivity is represented by a hypothetical sodium chloride electrolyte. This study introduces a modified version of early LSU models. This modified model eliminates a questionable assumption incorporated in all previous shaly sand models. Previous models use same formation resistivity factor for all terms in the model. The proposed model considers that the electric current follows the effective porosity path in the term representing the free electrolyte and follows the clay porosity path in the term representing bound water. The differentiation between the two paths is accomplished by using two different formation factors one in the free water and another in the bound water term of the model. It also used two different cementation exponents to express formation factors in terms of porosity. The validity of the new model was checked using cation exchange capacities measured on core samples and drill cuttings. Calculated cation exchange capacities display good agreement with the measured cation exchange capacities. The water saturation calculated using the new model are more representative of hydrocarbon potential of the zones of interest. In addition, cation exchange capacity calculated using this modified model and log data acquired during drilling has shown potential for diagnosis of pending bit balling of PDC bits drilled with water based mud in overpressured shale.

  11. Electron Spin Resonance Spectroscopic Studies of Radical Cation Reactions.

    NASA Astrophysics Data System (ADS)

    Dai, Sheng

    1990-01-01

    A spin Hamiltonian suitable for theoretical analyses of ESR spectra in this work is derived by using the general effective Hamiltonian theory in the usual Schrodinger representation. The Permutation Indices method is extended to obtain the dynamic exchange equations used in ESR lineshape simulation. The correlation between beta-hydrogen coupling constants and their geometric orientations is derived through the use of a perturbation method. The three electron bond model is extended to rationalize unimolecular rearrangements of radical cations. The ring-closed radical cations of 9,10-octalin oxide and syn-sesquinorbornene oxide have been characterized by ESR spectroscopy in the CFCl_3 matrix at low temperature. The ESR spectra of the former radical cation exhibit a novel alternating linewidth effect arising from an internal relation between the coupling constants for the four equivalent pairs of hydrogens. The self-electron-transfer rate constants between the methyl viologen dication and cation have been determined by dynamic ESR lineshape simulations at room temperature in allyl alcohol, water, methanol and propargyl alcohol solvents. The radical cation formed by the radiolytic oxidation of allylamine in Freon matrices at 77 K is shown to be the 3-iminiopropyl distonic species(3-iminium-1-propyl radical) resulting from a symmetry-allowed 1,2-hydrogen shift in the parent radical cation. The nucleophilic endocyclization of the but-3-en-1-ol radical cation to the protonated tetrahydrofuran -3-yl radical was observed in the radiolytic oxidation of but-3-en-1-ol in Freon matrices. ESR studies of the radiolytic oxidation of 1,5-hexadiyne have resulted in the first spectroscopic characterization of the radical cation Cope rearrangement, the 1,5-hexadiyne radical cation isomerizing to the 1,2,4,5 -hexatetraene radical cation. ESR studies show that the symmetric(C_{rm 2v}) bicyclo (3.3.0) -octa-2,6-diene-4,8-diyl(a bridged 1,4 -bishomobenzene species) radical cation is

  12. Cation immobilization in pyrolyzed simulated spent ion exchange resins

    NASA Astrophysics Data System (ADS)

    Luca, Vittorio; Bianchi, Hugo L.; Manzini, Alberto C.

    2012-05-01

    Significant quantities of spent ion exchange resins that are contaminated by an assortment of radioactive elements are produced by the nuclear industry each year. The baseline technology for the conditioning of these spent resins is encapsulation in ordinary Portland cement which has various shortcomings none the least of which is the relatively low loading of resin in the cement and the poor immobilization of highly mobile elements such as cesium. The present study was conducted with cationic resin samples (Lewatit S100) loaded with Cs+, Sr2+, Co2+, Ni2+ in roughly equimolar proportions at levels at or below 30% of the total cation exchange capacity. Low temperature thermal treatment of the resins was conducted in inert (Ar), or reducing (CH4) gas atmospheres, or supercritical ethanol to convert the hydrated polymeric resin beads into carbonaceous materials that contained no water. This pyrolytic treatment resulted in at least a 50% volume reduction to give mechanically robust spherical materials. Scanning electron microscope investigations of cross-sections of the beads combined with energy dispersive analysis showed that initially all elements were uniformly distributed through the resin matrix but that at higher temperatures the distribution of Cs became inhomogeneous. Although Cs was found in the entire cross-section, a significant proportion of the Cs occurred within internal rings while a proportion migrated toward the outer surfaces to form a crustal deposit. Leaching experiments conducted in water at 25 °C showed that the divalent contaminant elements were very difficult to leach from the beads heated in inert atmospheres in the range 200-600 °C. Cumulative fractional loses of the order of 0.001 were observed for these divalent elements for temperatures below 500 °C. Regardless of the processing temperature, the cumulative fractional loss of Cs in water at 25 °C reached a plateau or steady-state within the first 24 h increasing only marginally up 120 h

  13. Controlling Cesium Cation Recognition via Cation Metathesis within and Ion Pair Receptor

    SciTech Connect

    Kim, Sung Kuk; Vargas-Zuniga, Gabriela; Hay, Benjamin; Young, Neil J; Delmau, Laetitia Helene; Lee, Prof. Chang-Hee; Kim, Jong Seung; Lynch, Vincent M.; Sessler, Jonathan L.

    2012-01-01

    Ion pair receptor 3 bearing an anion binding site and multiple cation binding sites has been synthesized and shown to function in a novel binding-release cycle that does not necessarily require displacement to effect release. The receptor forms stable complexes with the test cesium salts, CsCl and CsNO{sub 3}, in solution (10% methanol-d{sub 4} in chloroform-d) as inferred from {sup 1}H NMR spectroscopic analyses. The addition of KClO{sub 4} to these cesium salt complexes leads to a novel type of cation metathesis in which the 'exchanged' cations occupy different binding sites. Specifically, K{sup +} becomes bound at the expense of the Cs{sup +} cation initially present in the complex. Under liquid-liquid conditions, receptor 3 is able to extract CsNO{sub 3} and CsCl from an aqueous D{sub 2}O layer into nitrobenzene-d{sub 5} as inferred from {sup 1}H NMR spectroscopic analyses and radiotracer measurements. The Cs{sup +} cation of the CsNO{sub 3} extracted into the nitrobenzene phase by receptor 3 may be released into the aqueous phase by contacting the loaded nitrobenzene phase with an aqueous KClO{sub 4} solution. Additional exposure of the nitrobenzene layer to chloroform and water gives 3 in its uncomplexed, ion-free form. This allows receptor 3 to be recovered for subsequent use. Support for the underlying complexation chemistry came from single-crystal X-ray diffraction analyses and gas-phase energy-minimization studies.

  14. Ground state of naphthyl cation: Singlet or triplet?

    SciTech Connect

    Dutta, Achintya Kumar; Vaval, Nayana Pal, Sourav; Manohar, Prashant U.

    2014-03-21

    We present a benchmark theoretical investigation on the electronic structure and singlet-triplet(S-T) gap of 1- and 2-naphthyl cations using the CCSD(T) method. Our calculations reveal that the ground states of both the naphthyl cations are singlet, contrary to the results obtained by DFT/B3LYP calculations reported in previous theoretical studies. However, the triplet states obtained in the two structural isomers of naphthyl cation are completely different. The triplet state in 1-naphthyl cation is (π,σ) type, whereas in 2-naphthyl cation it is (σ,σ{sup ′}) type. The S-T gaps in naphthyl cations and the relative stability ordering of the singlet and the triplet states are highly sensitive to the basis-set quality as well as level of correlation, and demand for inclusion of perturbative triples in the coupled-cluster ansatz.

  15. 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.

  16. 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.

  17. Solvent effect on cation-π interactions with Al3+.

    PubMed

    Larrucea, Julen

    2012-09-01

    Cation-π interactions are known to be one of the strongest noncovalent forces in the gas phase, but they rarely occur in a fully solvated environment. The present work used two different ab initio molecular dynamics-based approaches to describe the correlation between the strength of the cation-π interactions and the number of water molecules surrounding the cation. Five different complexes between an aluminum cation and different molecules containing aromatic rings were studied, and the degree of hydration of each complex was varied. Results indicated that cation-π interactions vanish when the aluminum cation is surrounded by more than three water molecules. The results also highlighted the influence of -OH ligands on the interaction strength. PMID:22581060

  18. Cation control of energetics on dye-sensitized nanocrystalline TiO2 for solar cells

    NASA Astrophysics Data System (ADS)

    Stux, Arnold M.

    Regenerative solar cells based on nanocrystalline TiO2 (anatase) and the dye Ru(deeb)(bpy)2(PF6)2, where deeb is 4,4'-(CO2CH2CH3)2-2,2 '-bipyridine and bpy is 2,2'-bipyridine, have increased efficiency when in the presence of a high concentration of cations with a large charge-to-radius ratio. Concentration-dependent photoluminescence (PL) quenching and increased quantum yield for interfacial charge separation have been explored for mono- and divalent cations by absorbance, time-resolved and steady-state PL. Cation adsorption stabilizes TiO2 acceptor states resulting in energetically favorable electron transfer from the dye into the semiconductor conduction band. Quenching of the PL of excited states is reversible. A new luminescence approach for sensing alkali and alkaline earth metal cations utilizes the surface-adsorption/desorption induced energetic shifts of a semiconductor conduction band to alter the electron transfer quenching efficiency of a photoluminescent dye such as Ru(deeb)(bpy)2(PF 6)2 anchored to TiO2 nanoparticles. This approach yields intensity, lifetime, and wavelength-ratiometric calcium ion sensors that are sensitive to 5 x 10-4 M concentrations. In situ photoluminescence of a regenerative solar cell has been demonstrated as a probe of injection and efficiencies. The smaller the alkali cation, the higher the photocurrent and the more quenched the photoluminescence. The extent of quenching in 0.1 M iodide/0.01 M iodine electrolytes was 10-fold with LiI and 3-fold with NaI. A millimolar threshold concentration is observed for Li+ at which point a red shift in absorbance and photoluminescence spectra concomitant with significant static and dynamic quenching occurs. For Na+, the threshold concentration for observable red shift is more than an order of magnitude higher than for Li+. Cation adsorption was also observed on planar TiO2 surfaces in the absence of dye. The flat band potentials of single crystal TiO 2 (rutile) with cations in propylene

  19. Observation of separate cation and anion electrophoretic mobilities in pure ionic liquids

    NASA Astrophysics Data System (ADS)

    Zhang, Zhiyang; Madsen, Louis A.

    2014-02-01

    Ionic liquids (ILs) continue to show relevance in many fields, from battery electrolytes, to carbon capture, to advanced separations. These highly ion-dense fluids present unique challenges in understanding their electrochemical properties due to deviations in behavior from existing electrolyte theories. Here we present a novel characterization of ILs using electrophoretic NMR (ENMR) to determine separate cation and anion mobilities. This method uses an applied electric field coincident with a pulsed magnetic field gradient to encode the E-field driven flow into NMR signals for cations (1H) and anions (19F). We describe the detailed design of these experiments, including quantitative analysis of artifact mitigation and necessary control experiments. We then explore mobilities and diffusion coefficients for two representative ILs: 1-ethyl-3-methyl imidazolium tetrafluoroborate ([C2mim][BF4]) and 1-ethyl-3-methyl imidazolium trifluoromethanesulfonate ([C2mim][TfO]). We further use the individual ion mobilities to calculate the bulk net conductivity, which closely agrees with bulk conductivity measurements obtained using impedance spectroscopy. These observations represent the first reliable measurements of cation and anion mobilities in pure ILs, with errors of ±7%. We discuss this advanced experimental methodology in detail, as well as implications of these sensitive measurements for understanding conduction mechanisms in ion-dense electrolytes.

  20. Observation of separate cation and anion electrophoretic mobilities in pure ionic liquids.

    PubMed

    Zhang, Zhiyang; Madsen, Louis A

    2014-02-28

    Ionic liquids (ILs) continue to show relevance in many fields, from battery electrolytes, to carbon capture, to advanced separations. These highly ion-dense fluids present unique challenges in understanding their electrochemical properties due to deviations in behavior from existing electrolyte theories. Here we present a novel characterization of ILs using electrophoretic NMR (ENMR) to determine separate cation and anion mobilities. This method uses an applied electric field coincident with a pulsed magnetic field gradient to encode the E-field driven flow into NMR signals for cations ((1)H) and anions ((19)F). We describe the detailed design of these experiments, including quantitative analysis of artifact mitigation and necessary control experiments. We then explore mobilities and diffusion coefficients for two representative ILs: 1-ethyl-3-methyl imidazolium tetrafluoroborate ([C2mim][BF4]) and 1-ethyl-3-methyl imidazolium trifluoromethanesulfonate ([C2mim][TfO]). We further use the individual ion mobilities to calculate the bulk net conductivity, which closely agrees with bulk conductivity measurements obtained using impedance spectroscopy. These observations represent the first reliable measurements of cation and anion mobilities in pure ILs, with errors of ±7%. We discuss this advanced experimental methodology in detail, as well as implications of these sensitive measurements for understanding conduction mechanisms in ion-dense electrolytes. PMID:24588161

  1. 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. PMID:26444443

  2. Heat conduction in conducting polyaniline nanofibers

    NASA Astrophysics Data System (ADS)

    Nath, Chandrani; Kumar, A.; Syu, K.-Z.; Kuo, Y.-K.

    2013-09-01

    Thermal conductivity and specific heat of conducting polyaniline nanofibers are measured to identify the nature of heat carrying modes combined with their inhomogeneous structure. The low temperature thermal conductivity results reveal crystalline nature while the high temperature data confirm the amorphous nature of the material suggesting heterogeneous model for conducting polyaniline. Extended acoustic phonons dominate the low temperature (<100 K) heat conduction, while localized optical phonons hopping, assisted by the extended acoustic modes, account for the high temperature (>100 K) heat conduction.

  3. Transport of a reactive tracer in saturated alluvium described using a three-component cation-exchange model.

    PubMed

    Sullivan, Enid J; Reimus, Paul W; Counce, Dale A

    2003-01-01

    A weakly sorbing cation, lithium, will be used as a reactive tracer in upcoming field tracer tests in the saturated alluvium south of Yucca Mountain, Nevada. One objective of the field tests is to determine how well field-scale reactive transport can be predicted using transport parameters derived from laboratory experiments. This paper describes several laboratory lithium batch sorption and column transport experiments that were conducted using ground water and alluvium obtained from the site of the planned field tests. In the batch experiments, isotherms were determined over 2.5 orders of magnitude of lithium concentrations, corresponding to the range expected in the field tests. In addition to measuring equilibrium lithium concentrations, concentrations of other cations, namely Na(+), K(+), and Ca(2+), were measured in the batch tests to determine Li(+)-exchangeable equilibria. This information was used in conjunction with alluvium cation exchange capacity measurements to parameterize a three-component cation-exchange model (EQUIL) that describes lithium sorption in the alluvium system. This model was then applied to interpret the transport behavior of lithium ion in saturated alluvium column tests conducted at three different lithium bromide injection concentrations. The concentrations were selected such that lithium ion either dominated, accounted for a little over half, or accounted for only a small fraction of the total cation equivalents in the injection solution. Although tracer breakthrough curves differed significantly under each of these conditions, with highly asymmetric responses occurring at the highest injection concentrations, the three-component cation-exchange model reproduced the observed transport behavior of lithium and the other cations in each case with a similar set of model parameters. In contrast, a linear K(d)-type sorption model could only match the lithium responses at the lowest injection concentration. The three-component model will

  4. Infrared spectroscopic investigations of cationic ethanol, propanol, and butanol

    NASA Astrophysics Data System (ADS)

    Matsuda, Yoshiyuki; Harigaya, Hiroyuki; Xie, Min; Takahashi, Kaito; Fujii, Asuka

    2015-11-01

    Infrared spectroscopy of the alcohol cations of ethanol, propanol, and butanol was performed to investigate their structures and hyperconjugation mechanisms. In the ethanol cation, the Csbnd C bond hyperconjugates with the singly occupied molecular orbital (SOMO) at the oxygen atom, so that the Csbnd C bond weakens and the bond length elongates. Multiple hyperconjugations among SOMO, the Csbnd C bond, and the end Csbnd H bond occur in the propanol cation and enhance the acidity of the Csbnd H bond through the delocalization of its bonding σ electron. The butanol cation forms the oxonium-type structure through the proton transfer from the terminal CH bond.

  5. Supramolecular Explorations: Exhibiting the Extent of Extended Cationic Cyclophanes.

    PubMed

    Dale, Edward J; Vermeulen, Nicolaas A; Juríček, Michal; Barnes, Jonathan C; Young, Ryan M; Wasielewski, Michael R; Stoddart, J Fraser

    2016-02-16

    Acting as hosts, cationic cyclophanes, consisting of π-electron-poor bipyridinium units, are capable of entering into strong donor-acceptor interactions to form host-guest complexes with various guests when the size and electronic constitution are appropriately matched. A synthetic protocol has been developed that utilizes catalytic quantities of tetrabutylammonium iodide to make a wide variety of cationic pyridinium-based cyclophanes in a quick and easy manner. Members of this class of cationic cyclophanes with boxlike geometries, dubbed Ex(n)Boxm(4+) for short, have been prepared by altering a number of variables: (i) n, the number of "horizontal" p-phenylene spacers between adjoining pyridinium units, to modulate the "length" of the cavity; (ii) m, the number of "vertical" p-phenylene spacers, to modulate the "width" of the cavity; and (iii) the aromatic linkers, namely, 1,4-di- and 1,3,5-trisubstituted units for the construction of macrocycles (ExBoxes) and macrobicycles (ExCages), respectively. This Account serves as an exploration of the properties that emerge from these structural modifications of the pyridinium-based hosts, coupled with a call for further investigation into the wealth of properties inherent in this class of compounds. By variation of only the aforementioned components, the role of these cationic receptors covers ground that spans (i) synthetic methodology, (ii) extraction and sequestration, (iii) catalysis, (iv) molecular electronics, (v) physical organic chemistry, and (vi) supramolecular chemistry. Ex(1)Box(4+) (or simply ExBox(4+)) has been shown to be a multipurpose receptor capable of binding a wide range of polycyclic aromatic hydrocarbons (PAHs), while also being a suitable component in switchable mechanically interlocked molecules. Additionally, the electronic properties of some host-guest complexes allow the development of artificial photosystems. Ex(2)Box(4+) boasts the ability to bind both π-electron-rich and -poor aromatic

  6. Univalent-cation-elicited acidification by yeasts.

    PubMed

    Kotyk, A; Georghiou, G

    1994-08-01

    Addition of univalent cations to sugar-metabolizing Saccharomyces cerevisiae, Schizosaccharomyces pombe and Lodderomyces elongisporus brought about a powerful acidification of the external medium with rates up to nearly 20 nmol H+ per min per mg dry wt. in S. cerevisiae, over 15 nmol in S. pombe, and 4.7 nmol in L. elongisporus. These rates were as much as 20 times, 5.5 times and 10.3 times, respectively. higher than in the absence of K+. Use of galactose-induced cells, of H(+)-ATPase-deficient mutants and observations over the entire growth curve indicated that the K+ effect on H+ extrusion is not connected with the H(+)-ATPase function as such but rather depends on metabolic reactions producing ATP. The effect has apparently nothing to do with the electrical potential across the plasma membrane. PMID:7804140

  7. Cation Diffusion Facilitator family: Structure and function.

    PubMed

    Kolaj-Robin, Olga; Russell, David; Hayes, Kevin A; Pembroke, J Tony; Soulimane, Tewfik

    2015-05-22

    The Cation Diffusion Facilitators (CDFs) form a family of membrane-bound proteins capable of transporting zinc and other heavy metal ions. Involved in metal tolerance/resistance by efflux of ions, CDF proteins share a two-modular architecture consisting of a transmembrane domain (TMD) and C-terminal domain (CTD) that protrudes into the cytoplasm. Discovery of a Zn²⁺ and Cd²⁺ CDF transporter from a marine bacterium Maricaulis maris that does not possess the CTD questions current perceptions regarding this family of proteins. This article describes a new, CTD-lacking subfamily of CDFs and our current knowledge about this family of proteins in the view of these findings. PMID:25896018

  8. Cell Penetrating Peptides and Cationic Antibacterial Peptides

    PubMed Central

    Rodriguez Plaza, Jonathan G.; Morales-Nava, Rosmarbel; Diener, Christian; Schreiber, Gabriele; Gonzalez, Zyanya D.; Lara Ortiz, Maria Teresa; Ortega Blake, Ivan; Pantoja, Omar; Volkmer, Rudolf; Klipp, Edda; Herrmann, Andreas; Del Rio, Gabriel

    2014-01-01

    Cell penetrating peptides (CPP) and cationic antibacterial peptides (CAP) have similar physicochemical properties and yet it is not understood how such similar peptides display different activities. To address this question, we used Iztli peptide 1 (IP-1) because it has both CPP and CAP activities. Combining experimental and computational modeling of the internalization of IP-1, we show it is not internalized by receptor-mediated endocytosis, yet it permeates into many different cell types, including fungi and human cells. We also show that IP-1 makes pores in the presence of high electrical potential at the membrane, such as those found in bacteria and mitochondria. These results provide the basis to understand the functional redundancy of CPPs and CAPs. PMID:24706763

  9. Cationic nanofibrillar cellulose with high antibacterial properties.

    PubMed

    Chaker, Achraf; Boufi, Sami

    2015-10-20

    Cationic nanofibrillar cellulose (C-NFC) has been prepared via a high pressure homogenization using quaternized cellulose fibers with glycidyltrimethylammonium chloride. It has been shown that the quaternization of dried softwood pulp facilitated the defibrillation processes and prevented clogging of the homogenizer. The effects of the trimethylammonium chloride content on the fibrillation yield, the transparency degree of the gel, the rheological behavior of the NFC suspension and their electrokinetic properties were investigated. AFM observation showed that the NFC suspension consisted of individualized cellulose I nanofibrils 4-5nm in width and length in the micronic scale. In addition to their strong reinforcing potential, the inclusion of C-NFC into a polymer matrix was shown to efficiently enhance the antibacterial activity. The reinforcing potential of C-NFC, studied by dynamic mechanical analysis (DMA), was compared to anionic NFC and the difference was explained in terms of the nanofibrils capacities to build up a strong networks held by hydrogen bonding. PMID:26256179

  10. Chemically modified polymeric resins for separation of cations, organic acids, and small polar moleculea by high performance liquid chromatography

    SciTech Connect

    Morris, J.B.

    1993-07-01

    This thesis is divided into 4 parts: a review, ion chromatography of metal cations on carboxylic resins, separation of hydrophilic organic acids and small polar compounds on macroporous resin columns, and use of eluent modifiers for liquid chromatographic separation of carboxylic acids using conductivity detection.

  11. Antiviral effect of cationic compounds on bacteriophages

    PubMed Central

    Ly-Chatain, Mai H.; Moussaoui, Saliha; Vera, Annabelle; Rigobello, Véronique; Demarigny, Yann

    2013-01-01

    The antiviral activity of several cationic compounds – cetyltrimethylammonium bromide (CTAB), chitosan, nisin, and lysozyme – was investigated on the bacteriophage c2 (DNA head and non-contractile tail) infecting Lactococcus strains and the bacteriophage MS2 (F-specific RNA) infecting E. coli. Firstly, these activities were evaluated in a phosphate buffer pH 7 – 10 mM. The CTAB had a virucidal effect on the Lactococcus bacteriophages, but not on the MS2. After 1 min of contact with 0.125 mM CTAB, the c2 population was reduced from 6 to 1.5 log(pfu)/mL and completely deactivated at 1 mM. On the contrary, chitosan inhibited the MS2 more than it did the bacteriophages c2. No antiviral effect was observed for the nisin or the lysozyme on bacteriophages after 1 min of treatment. A 1 and 2.5 log reduction was respectively observed for nisin and lysozyme when the treatment time increased (5 or 10 min). These results showed that the antiviral effect depended both on the virus and structure of the antimicrobial compounds. The antiviral activity of these compounds was also evaluated in different physico-chemical conditions and in complex matrices. The antiviral activity of CTAB was impaired in acid pH and with an increase of the ionic strength. These results might be explained by the electrostatic interactions between cationic compounds and negatively charged particles such as bacteriophages or other compounds in a matrix. Milk proved to be protective suggesting the components of food could interfere with antimicrobial compounds. PMID:23487495

  12. Adsorption of a water soluble cationic dye into a cationic Langmuir monolayer

    NASA Astrophysics Data System (ADS)

    Shil, Ashis; Hussain, S. A.; Bhattacharjee, D.

    2015-05-01

    This communication reports the successful adsorption of a water soluble cationic fluorescent dye Rhodamine B (RhB) into a cationic Langmuir monolayer of Octadecylamine (ODA). Anionic nano clay platelets Hectorite played an important role in the process of adsorption. Surface pressure vs. area per molecule (π-A) isotherms were studied to monitor the adsorption process. In-situ fluorescence Imaging Microscopic (FIM) technique was employed to visualize the domain structures formed at the air-water interface. Atomic Force Microscopic (AFM) image of the monolayer Langmuir-Blodgett (LB) films were taken to study the morphology and ultrastructure of the film. Detailed spectroscopic investigations were carried out on the mono- and multilayer Langmuir-Blodgett (LB) films.

  13. Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

    DOE PAGESBeta

    Kim, Michelle J.; Zoerb, Matthew C.; Campbell, Nicole R.; Zimmermann, Kathryn J.; Blomquist, Byron W.; Huebert, Barry J.; Bertram, Timothy H.

    2016-01-01

    Benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e., DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical-ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt−1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a much weaker electric field, demonstrated that ion–molecule reactions likely proceed through a combination of ligand-switching and directmore » charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (< 25 %) was observed for the detection of β-caryophyllene, a bicyclic sesquiterpene. The in-field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer, where measurements from the two instruments were highly correlated (R2 > 0.95, 10 s averages) over a wide range of sampling conditions.« less

  14. Ferromagnetic Conducting Lignosulfonic Acid-doped Polyaniline Nanocomposites

    NASA Technical Reports Server (NTRS)

    Viswansthan, Tito (Inventor); Berry, Brian (Inventor)

    2004-01-01

    A conductive ferromagnetic composition of matter comprising sulfonated lignin or a sulfonated polyflavonoid, or derivatives thereof, and ferromagnetic iron oxide particles is disclosed. Among the uses of the composition is to shield electromagnetic radiation. The ferromagnetic iron oxide particles of the composition are surprisingly stable to acid, and are easily and inexpensively formed from iron cations in solution.

  15. Does cation break the cyano bond? A critical evaluation of nitrile-cation interaction.

    PubMed

    Woi, Pei Meng; Bakar, Maizathul Akmam A; Rosli, Ahmad Nazmi; Lee, Vannajan Sanghiran; Ahmad, Mohd Rais; Zain, Sharifuddin; Alias, Yatimah

    2014-05-01

    DFT and G4 results reveal that cations display the following trends in imparting its positive charge to acrylonitrile; H⁺ > Li⁺ > Na⁺ > K⁺ for group I and Be²⁺ > Mg²⁺ > Ca²⁺ for group II. Solvation by water molecules and interaction with cation make the cyano bond more polarized and exhibits ketene-imine character. Bond order in nitrile-cation complexes has been predicted based on the s character of the covalent bond orbitals. Mulliken, CHELPG, and NPA charges are in good agreement in predicting positive charge buildup and GIAO nuclear deshileding on C1. G4 enthalpies show that Mg²⁺ is more strongly bound to acrylonitrile than to acetonitrile by 3 kcal mol⁻¹, and the proton affinity of the former is higher by 0.8 kcal mol⁻¹. G4 enthalpies of reductions support prior experimental observation that metalated conjugated nitriles show enhanced reactivity toward weak nucleophiles to afford Michael addition products. PMID:24770548

  16. 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

  17. 4-Spiro[2.n]alkyl cations and their rearrangements.

    PubMed

    Prakash, G K; Fung, A P; Olah, G A; Rawdah, T N

    1987-08-01

    A series of 4-spiro[2.n]alkanols, where n = 3-7, were ionized in either FSO3H x SbF5/SO2ClF or SbF5/SO2ClF at -78 degrees C and -130 degrees C. The resulting solutions were studied by 13C NMR spectroscopy over the temperature range of -130 degrees C to -10 degrees C. The 4-spiro[2.5]octanol gave the expected static 4-spiro[2.5]octyl cation, which can be considered as a long-lived secondary cyclohexyl cation stabilized by an adjacent spirocyclopropane ring. The same spiro[2.5]octyl cation was also obtained by ionization of isomeric bicyclo[4.2.0]octan-1-ol and bicyclo[4.1.0]heptyl-1-methanol. The static spiro[2.5]-octyl cation was found to rearrange to the equilibrating 1-bicyclo[3.3.0]octyl cation above -10 degrees C. On the other hand, the 4-spiro[2.4]heptanol gave the rearranged 1-methylcyclohexenyl cation. The spiro[2.6]nonanol gave directly the equilibrating 1-bicyclo[4.3.0]nonyl cation. The other 4-spiro[2.n]-alkanols (n = 3 and 7) gave unidentifiable polymeric products. The ionization of 3-spirocyclopropyl-2-norbornanol yields only the rearranged 2-methylbicyclo[3.2.1]oct-3-ene-2-yl cation. PMID:3474642

  18. 4-Spiro[2.n]alkyl cations and their rearrangements.

    PubMed Central

    Prakash, G K; Fung, A P; Olah, G A; Rawdah, T N

    1987-01-01

    A series of 4-spiro[2.n]alkanols, where n = 3-7, were ionized in either FSO3H x SbF5/SO2ClF or SbF5/SO2ClF at -78 degrees C and -130 degrees C. The resulting solutions were studied by 13C NMR spectroscopy over the temperature range of -130 degrees C to -10 degrees C. The 4-spiro[2.5]octanol gave the expected static 4-spiro[2.5]octyl cation, which can be considered as a long-lived secondary cyclohexyl cation stabilized by an adjacent spirocyclopropane ring. The same spiro[2.5]octyl cation was also obtained by ionization of isomeric bicyclo[4.2.0]octan-1-ol and bicyclo[4.1.0]heptyl-1-methanol. The static spiro[2.5]-octyl cation was found to rearrange to the equilibrating 1-bicyclo[3.3.0]octyl cation above -10 degrees C. On the other hand, the 4-spiro[2.4]heptanol gave the rearranged 1-methylcyclohexenyl cation. The spiro[2.6]nonanol gave directly the equilibrating 1-bicyclo[4.3.0]nonyl cation. The other 4-spiro[2.n]-alkanols (n = 3 and 7) gave unidentifiable polymeric products. The ionization of 3-spirocyclopropyl-2-norbornanol yields only the rearranged 2-methylbicyclo[3.2.1]oct-3-ene-2-yl cation. PMID:3474642

  19. Cation Effects on Nitrate Mobility in an Unsaturated Soil

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Transient, unsaturated, horizontal column experiments were carried out with a computer controlled syringe pump for the purpose of assessing counterion (accompanying cation) effects on nitrate (NO3-) mobility in unsaturated soil. A loam soil with calcium dominated cation exchange sites was used in al...

  20. Photodynamic Inactivation of Bacteria and Biofilms Using Cationic Bacteriochlorins

    NASA Astrophysics Data System (ADS)

    Meerovich, G. A.; Tiganova, I. G.; Makarova, E. A.; Meerovich, I. G.; Romanova Ju., M.; Tolordova, E. R.; Alekseeva, N. V.; Stepanova, T. V.; Yu, Koloskova; Luk'anets, E. A.; Krivospitskaya, N. V.; Sipailo, I. P.; Baikova, T. V.; Loschenov, V. B.; Gonchukov, S. A.

    2016-02-01

    This work is devoted to the study of two new synthetic bacteriochlorins with four and eight cationic substitutes as the photosensitizers in the photodynamic process. The spectral and antibacterial properties of these photosensitizers in saline solution were investigated. It is shown, that the aggregation ability decreases and the antibacterial efficiency grows as the cationic substitute number increases.

  1. High capacity nickel battery material doped with alkali metal cations

    DOEpatents

    Jackovitz, John F.; Pantier, Earl A.

    1982-05-18

    A high capacity battery material is made, consisting essentially of hydrated Ni(II) hydroxide, and about 5 wt. % to about 40 wt. % of Ni(IV) hydrated oxide interlayer doped with alkali metal cations selected from potassium, sodium and lithium cations.

  2. CATION EXCHANGE METHOD FOR THE RECOVERY OF PROTACTINIUM

    DOEpatents

    Studier, M.H.; Sullivan, J.C.

    1959-07-14

    A cation exchange prccess is described for separating protactinium values from thorium values whereby they are initially adsorbed together from an aqueous 0.1 to 2 N hydrochloric acid on a cation exchange resin in a column. Then selectively eluting the thorium by an ammonium sulfate solution and subsequently eluting the protactinium by an oxalate solution.

  3. Effects of cationic hydroxyethyl cellulose on glucose tolerance and obesity

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Cholestyramine is a cationic polymer prescribed to lower cholesterol in humans. We investigated the effects of cationic hydroxyethyl cellulose (cHEC) on weight loss and metabolic disorders associated with obesity using both hamster and diet-induced obese mouse models. Golden Syrian hamsters and ob...

  4. Kinetic Monte Carlo Simulation of Cation Diffusion in Low-K Ceramics

    NASA Technical Reports Server (NTRS)

    Good, Brian

    2013-01-01

    Low thermal conductivity (low-K) ceramic materials are of interest to the aerospace community for use as the thermal barrier component of coating systems for turbine engine components. In particular, zirconia-based materials exhibit both low thermal conductivity and structural stability at high temperature, making them suitable for such applications. Because creep is one of the potential failure modes, and because diffusion is a mechanism by which creep takes place, we have performed computer simulations of cation diffusion in a variety of zirconia-based low-K materials. The kinetic Monte Carlo simulation method is an alternative to the more widely known molecular dynamics (MD) method. It is designed to study "infrequent-event" processes, such as diffusion, for which MD simulation can be highly inefficient. We describe the results of kinetic Monte Carlo computer simulations of cation diffusion in several zirconia-based materials, specifically, zirconia doped with Y, Gd, Nb and Yb. Diffusion paths are identified, and migration energy barriers are obtained from density functional calculations and from the literature. We present results on the temperature dependence of the diffusivity, and on the effects of the presence of oxygen vacancies in cation diffusion barrier complexes as well.

  5. 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. PMID:7858123

  6. Synthesis and properties of polymeric cation conductors and amphiphilic star polymers

    SciTech Connect

    Zho, Guangbin

    1992-12-31

    Polymeric alkali ion conductors consisting of a comblike polysiloxane with oligo-oxyethylene side chains and pendant sulfonate groups were synthesized by the quantitative hydrosilylation of an allyl methoxy-polyethylene glycol and allyl glycidyl ether with polyhydrogenmethyl-siloxane, followed by the sulfonation of the epoxy group. The addition of Si-H is chiefly to the B-vinyl carbon and the sulfonation reaction is quantitative. DSC and conductivity measurements show that these materials are essentially amorphous and their cation conducting behavior can be interpreted by a VTF type equation. Due to the tightness of the alkali sulfonate ion pairs the conductivity of these polymers is low compared to that of dual polymer electrolytes containing LiClO{sub 4} or LiCF{sub 3}SO{sub 3} salt. However, conductivities of up to 10{sup {minus}5} S cm{sup {minus}1} at 25{degrees}C can be achieved by adding cation chelating ligands such as tetraethylene glycol. The effect of cation, temperature, ion content, glass transition temperature, and additives on the conductivity of these materials is discussed. Well-defined multifunctional isocyantes are obtained in high purity and quantitative yield by hydrosilylation of m-isopropenyl-{alpha}, {alpha}-dimethylbenzyl isocyanate (m-TMI) with cyclic and acyclic hydrogen-methylsiloxanes. The products were exclusively result from {beta}-addition of Si-H to the double bond in m-TMI. The polyisocyanates were reacted with methoxypolyethylene glycols (MPEG) and with nonlphenoxypolyethylene glycols (NPPEG) to yield amphiphilic star polymers with a precise number of arms. Amphiphilic star homopolmers made from MPEG form micelles in water. Star polymers with NPPEG arms in aqueous solutions separate into two phases of constant composition, the condensed phase being an associative network resembling a hydrogel. Surface tension, viscosities, cloud points, salt binding and solubilities were determined and compared with linear or star polymers.

  7. Muscarinic receptor subtypes controlling the cationic current in guinea-pig ileal smooth muscle

    PubMed Central

    Zholos, Alexander V; Bolton, Thomas B

    1997-01-01

    The effects of muscarinic antagonists on cationic current evoked by activating muscarinic receptors with the stable agonist carbachol were studied by use of patch-clamp recording techniques in guinea-pig single ileal smooth muscle cells. Ascending concentrations of carbachol (3–300 μM) activated the cationic conductance in a concentration-dependent manner with conductance at a maximally effective carbachol concentration (Gmax) of 27.4±1.4 nS and a mean −log EC50 of 5.12±0.03 (mean±s.e.mean) (n=114). Muscarinic antagonists with higher affinity for the M2 receptor, methoctramine, himbacine and tripitramine, produced a parallel shift of the carbachol concentration-effect curve to the right in a concentration-dependent manner with pA2 values of 8.1, 8.0 and 9.1, respectively. All M3 selective muscarinic antagonists tested, 4-DAMP, p-F-HHSiD and zamifenacin, reduced the maximal response in a concentration-dependent and non-competitive manner. This effect could be observed even at concentrations which did not produce any increase in the EC50 for carbachol. At higher concentrations M3 antagonists shifted the agonist curve to the right, increasing the EC50, and depressed the maximum conductance response. Atropine, a non-selective antagonist, produced both reduction in Gmax (M3 effect) and significant increase in the EC50 (M2 effect) in the same concentration range. The depression of the conductance by 4-DAMP, zamifenacin and atropine could not be explained by channel block as cationic current evoked by adding GTPγS to the pipette (without application of carbachol) was unaffected. The results support the hypothesis that carbachol activates M2 muscarinic receptors so initiating the opening of cationic channels which cause depolarization; this effect is potentiated by an unknown mechanism when carbachol activates M3 receptors. As an increasing fraction of M3 receptors are blocked by an antagonist, the effects on cationic current of an increasing proportion of

  8. The Flocculating Cationic Polypetide from Moringa oleifera Seeds Damages Bacterial Cell Membranes by Causing Membrane Fusion.

    PubMed

    Shebek, Kevin; Schantz, Allen B; Sines, Ian; Lauser, Kathleen; Velegol, Stephanie; Kumar, Manish

    2015-04-21

    A cationic protein isolated from the seeds of the Moringa oleifera tree has been extensively studied for use in water treatment in developing countries and has been proposed for use in antimicrobial and therapeutic applications. However, the molecular basis for the antimicrobial action of this peptide, Moringa oleifera cationic protein (MOCP), has not been previously elucidated. We demonstrate here that a dominant mechanism of MOCP antimicrobial activity is membrane fusion. We used a combination of cryogenic electron microscopy (cryo-EM) and fluorescence assays to observe and study the kinetics of fusion of membranes in liposomes representing model microbial cells. We also conducted cryo-EM experiments on E. coli cells where MOCP was seen to fuse the inner and outer membranes. Coarse-grained molecular dynamics simulations of membrane vesicles with MOCP molecules were used to elucidate steps in peptide adsorption, stalk formation, and fusion between membranes. PMID:25845029

  9. Effects of Cations on Corrosion of Inconel 625 in Molten Chloride Salts

    NASA Astrophysics Data System (ADS)

    Zhu, Ming; Ma, Hongfang; Wang, Mingjing; Wang, Zhihua; Sharif, Adel

    2016-04-01

    Hot corrosion of Inconel 625 in sodium chloride, potassium chloride, magnesium chloride, calcium chloride and their mixtures with different compositions is conducted at 900°C to investigate the effects of cations in chloride salts on corrosion behavior of the alloy. XRD, SEM/EDS were used to analyze the compositions, phases, and morphologies of the corrosion products. The results showed that Inconel 625 suffers more severe corrosion in alkaline earth metal chloride molten salts than alkaline metal chloride molten salts. For corrosion in mixture salts, the corrosion rate increased with increasing alkaline earth metal chloride salt content in the mixture. Cations in the chloride molten salts mainly affect the thermal and chemical properties of the salts such as vapor pressure and hydroscopicities, which can affect the basicity of the molten salt. Corrosion of Inconel 625 in alkaline earth metal chloride salts is accelerated with increasing basicity.

  10. Cation Activation of the Basolateral Sodium-Potassium Pump in Turtle Colon

    PubMed Central

    Halm, D R; Dawson, D C

    1983-01-01

    The current generated by electrogenic sodium-potassium exchange at the basolateral membrane of the turtle colon can be measured directly in tissues that have been treated with serosal barium (to block the basolateral potassium conductance) and mucosal amphotericin B (to reduce the cation selectivity of the apical membrane). We studied the activation of this pump current by mucosal sodium and serosal potassium, rubidium, cesium, and ammonium. The kinetics of sodium activation were consistent with binding to three independent sites on the cytoplasmic side of the pump. The pump was not activated by cellular lithium ions. The kinetics of serosal cation activation were consistent with binding to two independent sites with the selectivity Rb > K > Cs > NH4. The properties and kinetics of the basolateral Na/K pump in the turtle colon are at least qualitatively similar to those ofthe well-characterized Na/K-ATPase of the human red blood cell . PMID:24244010

  11. Large electropositive cations as surfactants for the growth of polar epitaxial films

    NASA Astrophysics Data System (ADS)

    Cheung, Alfred K. C.; Elfimov, Ilya; Berciu, Mona; Sawatzky, George A.

    2015-03-01

    Using density functional theory (DFT) we demonstrate that the adsorption of large cations such as potassium or cesium facilitates the epitaxial growth of polar LaAlO3(LAO ) on SrTiO3(STO ). The low ionization potential of K favors efficient electron transfer to the STO conduction band and results in a two-dimensional electron gas which exactly compensates for the diverging potential with increasing layer thickness. For large cations like K or Cs, DFT total energy considerations show that they remain adsorbed on the LAO surface and do not enter substitutionally into LAO. These results suggest a scheme for growing clean LAO/STO interface systems, and polar systems in general, by performing the growth process in the presence of large, low ionization potential alkali-metal ions.

  12. ESR study of the aziridine and azetidine radical cations: evidence for the C. C ring-opened aziridine radical cation

    SciTech Connect

    Qin, X.Z.; Williams, F.

    1986-05-22

    The radical cations from aziridine and azetidine have been characterized by ESR spectroscopy following their generation in the solid state by ..gamma.. irradiation of dilute solutions of the parent compounds in the CFCl/sub 3/ matrix at 77 K. The ESR parameters of the azetidine radical cation are typical of those for nitrogen-centered amine radical cations such as Me/sub 2/NH*/sup +/. On the other hand, the radical cation formed from aziridine has very different ESR parameters that compare closely to those for the isoelectronic C...C ring-opened form of the oxirane radical cation and the allyl radical. The radical cation formed from azetidine is therefore assigned a ring-closed structure with the unpaired electron in a 2p/sub z/ orbital on nitrogen perpendicular to the ring plane, whereas the cation from aziridine is an allylic C...C ring-opened planar isomer with the unpaired electron in a nonbonding ..pi.. orbital centered mainly on the two end carbon atoms. The neutral 1-aziridinyl and 1-azetidinyl radicals have been detected as radical products following the ..gamma.. irradiation of the parent compounds in the CFCl/sub 2/CF/sub 2/Cl and CF/sub 3/CCl/sub 3/ matrices. In particular, the 1-azetidinyl radical is produced cleanly from the azetidine radical cation in the CFCl/sub 2/CF/sub 2/Cl matrix at ca. 100 K.

  13. Observation of radical cations by swiftness or by stealth.

    SciTech Connect

    Werst, D. W.; Trifunac, A. D.; Chemistry

    1998-01-01

    David W. Werst was born in Missouri and educated at the University of Missouri (B.S.) and the University of Minnesota (Ph.D.). His thesis work was carried out under the supervision of Paul Barbara and Ronald Gentry. He joined the Chemistry Division of Argonne National Laboratory in 1985 to conduct postdoctoral research in the group of Alexander Trifunac and has been a staff member of the Radiation and Photochemistry Group since 1989. His primary research interests are in the study of radical cation structure and reactivity and ionization processes in ordered and amorphous solids. Alexander D. Trifunac was born in Yugoslavia. He was educated at Columbia University (B.A.) and the University of Chicago (Ph.D.). His thesis work was on CIDNP, radical pair theory and experiments, with Gerhard L. Closs. He joined the Chemistry Division of Argonne National Laboratory in 1972 in a postdoctoral position. He is a senior scientist and is (since 1982) a group leader of the Radiation and Photochemistry Group. His research interests are in the study of chemistry of transient paramagnetic species involved in energy and charge-transfer processes occurring in radiolysis and in photoionization in liquids, glasses, and amorphous solids.

  14. The electrical conductivity of sodium polysulfide melts

    SciTech Connect

    Meihui Wang

    1992-06-01

    The sodium polysulfide melt has been described by a macroscopic model. This model considers the melt to be composed of sodium cations, monosulfide anions, and neutral sulfur solvent. The transport equations of concentrated-solution theory are used to derived the governing equations for this binaryelectrolyte melt model. These equations relate measurable transport properties to fundamental transport parameters. The focus of this research is to measure the electrical conductivity of sodium polysulfide melts and calculate one of fundamental transport parameters from the experimental data. The conductance cells used in the conductivity measurements are axisymmetric cylindrical cells with a microelectrode. The electrode effects, including double-layer capacity, charge transfer resistance, and concentration overpotential, were minimized by the use of the alternating current at an adequately high frequency. The high cell constants of the conductance cells not only enhanced the experimental accuracy but also made the electrode effects negligible. The electrical conductivities of sodium polysulfide Na{sub 2}S{sub 4} and Na{sub 2}S{sub 5} were measured as a function of temperature (range: 300 to 360{degree}C). Variations between experiments were only up to 2%. The values of the Arrhenius activation energy derived from the experimental data are about 33 kJ/mol. The fundamental transport parameter which quantifies the interaction within sodium cations and monosulfide anions are of interest and expected to be positive. Values of it were calculated from the experimental conductivity data and most of them are positive. Some negative values were obtained probably due to the experimental errors of transference number, diffusion coefficient, density or conductivity data.

  15. Origins of the p-Type Nature and Cation Deficiency in Cu2O and Related Materials

    SciTech Connect

    Raebiger, H.; Lany, S.; Zunger, A.

    2007-01-01

    While most of crystalline wide gap oxides are both stoichiometric and insulating, a handful of them including ZnO and In{sub 2}O{sub 3} are naturally anion-deficient and electron conductors. Even fewer of the oxides are naturally cation-deficient and hole conductors, the arch-type of which is Cu{sub 2}O. Based on first principles calculation of equilibrium nonstoichiometry and defect stability, we explain why the Cu{sup (I)}(d{sup 10}) oxide-based materials are both p-type and naturally cation-deficient, and why cation vacancies lead to delocalized, conductive states, whereas in other oxides (e.g., ZnO and MgO), they lead to localized, nonconductive states.

  16. Water Adsorption on Free Cobalt Cluster Cations.

    PubMed

    Kiawi, Denis M; Bakker, Joost M; Oomens, Jos; Buma, Wybren Jan; Jamshidi, Zahra; Visscher, Lucas; Waters, L B F M

    2015-11-01

    Cationic cobalt clusters complexed with water Con(+)-H2O (n = 6-20) are produced through laser ablation and investigated via infrared multiple photon dissociation (IR-MPD) spectroscopy in the 200-1700 cm(-1) spectral range. All spectra exhibit a resonance close to the 1595 cm(-1) frequency of the free water bending vibration, indicating that the water molecule remains intact upon adsorption. For n = 6, the frequency of this band is blue-shifted, but it gradually converges to the free water value with increasing cluster size. In the lower-frequency range (200-650 cm(-1)) the spectra contain several bands which show a very regular frequency evolution, suggesting that the exact cluster geometry has little effect on the water-surface interaction. Density functional theory (DFT) calculations are carried out at the OPBE/TZP level for three representative sizes (n = 6, 9, 13) and indicate that the vibrations responsible for the resonances correspond to bending and torsional modes between the cluster and water moieties. The potential energy surfaces describing these interactions are very shallow, making the calculated harmonic frequencies and IR intensities very sensitive to small geometrical perturbations. We conclude that harmonic frequency calculations on (local) minima structures provide insufficient information for these types of cluster complexes and need to be complemented with calculations that provide a more extensive sampling of the potential energy surface. PMID:26447780

  17. Therapeutic potential of cationic steroid antibacterials.

    PubMed

    Salmi, Chanaz; Brunel, Jean M

    2007-08-01

    Antibiotics were one of the great health successes of the 20th century. Antibiotics, both naturally derived and synthetic, have resulted in huge decreases in both morbidity and mortality from bacterial infections. As a consequence, the 'antibiotic age' has changed public expectations about the results of infectious disease. However, this has led to high levels of inappropriate prescribing, where antibiotics may be administered to fulfil patient expectations rather than for clinical benefit. Along with unwise uses in agriculture and elsewhere, this has contributed to recent rises in numbers of antibiotic-resistant bacteria. As a result, many commentators have described this as the end of the antibiotic age and the term 'superbug' has entered the common vocabulary for multi-drug-resistant bacteria such as vancomycin-resistant Enterococcus, multi-drug-resistant Staphylococcus aureus and multi-drug-resistant Pseudomonas aeruginosa. In this context, an attractive approach for the development of antibacterial agents is the use of a new class of cationic steroidal compounds mimicking polymyxin activities. The permeabilization properties of these agents of the outer membranes of Gram-negative bacteria are reported in this review, as well as a discussion of literature results. PMID:17685865

  18. Is Iodate a Strongly Hydrated Cation?

    SciTech Connect

    Baer, Marcel D.; Pham, Thai V.; Fulton, John L.; Schenter, Gregory K.; Balasubramanian, Mahalingam; Mundy, Christopher J.

    2011-10-06

    We show, through a combination of density function theory based molecular dynamics simulations (DFTMD) and experimental x-ray absorption fine structure spectroscopy (XAFS) studies, that the iodate ion (IO3-) is a zwitterion in solution. The local region adjoining the I atom is sufficiently electropositive that three hydrating waters are oriented with their O’s atoms directly interacting with the iodine atom at an I-OH2O distance of 2.95 Å. This is the orientation of water hydrating a cation. Further, approximately 2-3 water molecules hydrate each O of IO3 - through a single H atom in an orientation of the water that is expected for an anion at an IOH2O distance of 3.85 Å. We predict that this structure persists, although to a much lesser degree, for BrO3 -, and ClO3 -. This type of local microstructure profoundly affects the behavior of the "anion" at interfaces and how it interacts with other ionic species in solution.

  19. Antiendotoxin activity of cationic peptide antimicrobial agents.

    PubMed Central

    Gough, M; Hancock, R E; Kelly, N M

    1996-01-01

    The endotoxin from gram-negative bacteria consists of a molecule lipopolysaccharide (LPS) which can be shed by bacteria during antimicrobial therapy. A resulting syndrome, endotoxic shock, is a leading cause of death in the developed world. Thus, there is great interest in the development of antimicrobial agents which can reverse rather than promote sepsis, especially given the recent disappointing clinical performance of antiendotoxin therapies. We describe here two small cationic peptides, MBI-27 and MBI-28, which have both antiendotoxic and antibacterial activities in vitro and in vivo in animal models. We had previously demonstrated that these peptides bind to LPS with an affinity equivalent to that of polymyxin B. Consistent with this, the peptides blocked the ability of LPS and intact cells to induce the endotoxic shock mediator, tumor necrosis factor (TNF), upon incubation with the RAW 264.7 murine macrophage cell line. MBI-28 was equivalent to polymyxin B in its ability to block LPS induction of TNF by this cell line, even when added 60 min after the TNF stimulus. Furthermore, MBI-28 offered significant protection in a galactosamine-sensitized mouse model of lethal endotoxic shock. This protection correlated with the ability of MBI-28 to reduce LPS-induced circulating TNF by nearly 90% in this mouse model. Both MBI-27 and MBI-28 demonstrated antibacterial activity against gram-negative bacteria in vitro and in vivo against Pseudomonas aeruginosa infections in neutropenic mice. PMID:8945527

  20. A phosphotyrosine switch regulates organic cation transporters

    PubMed Central

    Sprowl, Jason A.; Ong, Su Sien; Gibson, Alice A.; Hu, Shuiying; Du, Guoqing; Lin, Wenwei; Li, Lie; Bharill, Shashank; Ness, Rachel A.; Stecula, Adrian; Offer, Steven M.; Diasio, Robert B.; Nies, Anne T.; Schwab, Matthias; Cavaletti, Guido; Schlatter, Eberhard; Ciarimboli, Giuliano; Schellens, Jan H. M.; Isacoff, Ehud Y.; Sali, Andrej; Chen, Taosheng; Baker, Sharyn D.; Sparreboom, Alex; Pabla, Navjotsingh

    2016-01-01

    Membrane transporters are key determinants of therapeutic outcomes. They regulate systemic and cellular drug levels influencing efficacy as well as toxicities. Here we report a unique phosphorylation-dependent interaction between drug transporters and tyrosine kinase inhibitors (TKIs), which has uncovered widespread phosphotyrosine-mediated regulation of drug transporters. We initially found that organic cation transporters (OCTs), uptake carriers of metformin and oxaliplatin, were inhibited by several clinically used TKIs. Mechanistic studies showed that these TKIs inhibit the Src family kinase Yes1, which was found to be essential for OCT2 tyrosine phosphorylation and function. Yes1 inhibition in vivo diminished OCT2 activity, significantly mitigating oxaliplatin-induced acute sensory neuropathy. Along with OCT2, other SLC-family drug transporters are potentially part of an extensive ‘transporter-phosphoproteome' with unique susceptibility to TKIs. On the basis of these findings we propose that TKIs, an important and rapidly expanding class of therapeutics, can functionally modulate pharmacologically important proteins by inhibiting protein kinases essential for their post-translational regulation. PMID:26979622

  1. Cationic Noncovalent Interactions: Energetics and Periodic Trends.

    PubMed

    Rodgers, M T; Armentrout, P B

    2016-05-11

    In this review, noncovalent interactions of ions with neutral molecules are discussed. After defining the scope of the article, which excludes anionic and most protonated systems, methods associated with measuring thermodynamic information for such systems are briefly recounted. An extensive set of tables detailing available thermodynamic information for the noncovalent interactions of metal cations with a host of ligands is provided. Ligands include small molecules (H2, NH3, CO, CS, H2O, CH3CN, and others), organic ligands (O- and N-donors, crown ethers and related molecules, MALDI matrix molecules), π-ligands (alkenes, alkynes, benzene, and substituted benzenes), miscellaneous inorganic ligands, and biological systems (amino acids, peptides, sugars, nucleobases, nucleosides, and nucleotides). Hydration of metalated biological systems is also included along with selected proton-based systems: 18-crown-6 polyether with protonated peptides and base-pairing energies of nucleobases. In all cases, the literature thermochemistry is evaluated and, in many cases, reanchored or adjusted to 0 K bond dissociation energies. Trends in these values are discussed and related to a variety of simple molecular concepts. PMID:26953819

  2. Repurposing Cationic Amphiphilic Antihistamines for Cancer Treatment.

    PubMed

    Ellegaard, Anne-Marie; Dehlendorff, Christian; Vind, Anna C; Anand, Atul; Cederkvist, Luise; Petersen, Nikolaj H T; Nylandsted, Jesper; Stenvang, Jan; Mellemgaard, Anders; Østerlind, Kell; Friis, Søren; Jäättelä, Marja

    2016-07-01

    Non-small cell lung cancer (NSCLC) is one of the deadliest cancers worldwide. In search for new NSCLC treatment options, we screened a cationic amphiphilic drug (CAD) library for cytotoxicity against NSCLC cells and identified several CAD antihistamines as inducers of lysosomal cell death. We then performed a cohort study on the effect of CAD antihistamine use on mortality of patients diagnosed with non-localized cancer in Denmark between 1995 and 2011. The use of the most commonly prescribed CAD antihistamine, loratadine, was associated with significantly reduced all-cause mortality among patients with non-localized NSCLC or any non-localized cancer when compared with use of non-CAD antihistamines and adjusted for potential confounders. Of the less frequently described CAD antihistamines, astemizole showed a similar significant association with reduced mortality as loratadine among patients with any non-localized cancer, and ebastine use showed a similar tendency. The association between CAD antihistamine use and reduced mortality was stronger among patients with records of concurrent chemotherapy than among those without such records. In line with this, sub-micromolar concentrations of loratadine, astemizole and ebastine sensitized NSCLC cells to chemotherapy and reverted multidrug resistance in NSCLC, breast and prostate cancer cells. Thus, CAD antihistamines may improve the efficacy of cancer chemotherapy. PMID:27333030

  3. Penetrating cations enhance uncoupling activity of anionic protonophores in mitochondria.

    PubMed

    Antonenko, Yuri N; Khailova, Ljudmila S; Knorre, Dmitry A; Markova, Olga V; Rokitskaya, Tatyana I; Ilyasova, Tatyana M; Severina, Inna I; Kotova, Elena A; Karavaeva, Yulia E; Prikhodko, Anastasia S; Severin, Fedor F; Skulachev, Vladimir P

    2013-01-01

    Protonophorous uncouplers causing a partial decrease in mitochondrial membrane potential are promising candidates for therapeutic applications. Here we showed that hydrophobic penetrating cations specifically targeted to mitochondria in a membrane potential-driven fashion increased proton-translocating activity of the anionic uncouplers 2,4-dinitrophenol (DNP) and carbonylcyanide-p-trifluorophenylhydrazone (FCCP). In planar bilayer lipid membranes (BLM) separating two compartments with different pH values, DNP-mediated diffusion potential of H(+) ions was enhanced in the presence of dodecyltriphenylphosphonium cation (C12TPP). The mitochondria-targeted penetrating cations strongly increased DNP- and carbonylcyanide m-chlorophenylhydrazone (CCCP)-mediated steady-state current through BLM when a transmembrane electrical potential difference was applied. Carboxyfluorescein efflux from liposomes initiated by the plastoquinone-containing penetrating cation SkQ1 was inhibited by both DNP and FCCP. Formation of complexes between the cation and CCCP was observed spectophotometrically. In contrast to the less hydrophobic tetraphenylphosphonium cation (TPP), SkQ1 and C12TPP promoted the uncoupling action of DNP and FCCP on isolated mitochondria. C12TPP and FCCP exhibited a synergistic effect decreasing the membrane potential of mitochondria in yeast cells. The stimulating action of penetrating cations on the protonophore-mediated uncoupling is assumed to be useful for medical applications of low (non-toxic) concentrations of protonophores. PMID:23626747

  4. Penetrating Cations Enhance Uncoupling Activity of Anionic Protonophores in Mitochondria

    PubMed Central

    Antonenko, Yuri N.; Khailova, Ljudmila S.; Knorre, Dmitry A.; Markova, Olga V.; Rokitskaya, Tatyana I.; Ilyasova, Tatyana M.; Severina, Inna I.; Kotova, Elena A.; Karavaeva, Yulia E.; Prikhodko, Anastasia S.; Severin, Fedor F.; Skulachev, Vladimir P.

    2013-01-01

    Protonophorous uncouplers causing a partial decrease in mitochondrial membrane potential are promising candidates for therapeutic applications. Here we showed that hydrophobic penetrating cations specifically targeted to mitochondria in a membrane potential-driven fashion increased proton-translocating activity of the anionic uncouplers 2,4-dinitrophenol (DNP) and carbonylcyanide-p-trifluorophenylhydrazone (FCCP). In planar bilayer lipid membranes (BLM) separating two compartments with different pH values, DNP-mediated diffusion potential of H+ ions was enhanced in the presence of dodecyltriphenylphosphonium cation (C12TPP). The mitochondria-targeted penetrating cations strongly increased DNP- and carbonylcyanide m-chlorophenylhydrazone (CCCP)-mediated steady-state current through BLM when a transmembrane electrical potential difference was applied. Carboxyfluorescein efflux from liposomes initiated by the plastoquinone-containing penetrating cation SkQ1 was inhibited by both DNP and FCCP. Formation of complexes between the cation and CCCP was observed spectophotometrically. In contrast to the less hydrophobic tetraphenylphosphonium cation (TPP), SkQ1 and C12TPP promoted the uncoupling action of DNP and FCCP on isolated mitochondria. C12TPP and FCCP exhibited a synergistic effect decreasing the membrane potential of mitochondria in yeast cells. The stimulating action of penetrating cations on the protonophore-mediated uncoupling is assumed to be useful for medical applications of low (non-toxic) concentrations of protonophores. PMID:23626747

  5. 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

    2015-02-01

    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. PMID:25569300

  6. Low conductivity and sintering-resistant thermal barrier coatings

    NASA Technical Reports Server (NTRS)

    Zhu, Dongming (Inventor); Miller, Robert A. (Inventor)

    2007-01-01

    A thermal barrier coating composition is provided. The composition has a base oxide, a primary stabilizer, and at least two additional cationic oxide dopants. Preferably, a pair of group A and group B defect cluster-promoting oxides is used in conjunction with the base and primary stabilizer oxides. The new thermal barrier coating is found to have significantly lower thermal conductivity and better sintering resistance. In preferred embodiments, the base oxide is selected from zirconia and hafnia. The group A and group B cluster-promoting oxide dopants preferably are selected such that the group A dopant has a smaller cationic radius than the primary stabilizer oxide, and so that the primary stabilizer oxide has a small cationic radius than that of the group B dopant.

  7. Low conductivity and sintering-resistant thermal barrier coatings

    NASA Technical Reports Server (NTRS)

    Zhu, Dongming (Inventor); Miller, Robert A. (Inventor)

    2006-01-01

    A thermal barrier coating composition is provided. The composition has a base oxide, a primary stabilizer, and at least two additional cationic oxide dopants. Preferably, a pair of group A and group B defect cluster-promoting oxides is used in conjunction with the base and primary stabilizer oxides. The new thermal barrier coating is found to have significantly lower thermal conductivity and better sintering resistance. In preferred embodiments, the base oxide is selected from zirconia and hafnia. The group A and group B cluster-promoting oxide dopants preferably are selected such that the group A dopant has a smaller cationic radius than the primary stabilizer oxide, and so that the primary stabilizer oxide has a small cationic radius than that of the group B dopant.

  8. Novel polymer electrolytes based on cationic polyurethane with different alkyl chain length

    NASA Astrophysics Data System (ADS)

    Liu, Libin; Wu, Xiwen; Li, Tianduo

    2014-03-01

    A series of comb-like cationic polyurethanes (PUs) were synthesized by quaternizing different bromoalkane (C2H5Br, C8H17Br, and C14H29Br) with polyurethane. Solid polymer electrolytes were prepared by complexes cationic PUs with different content of LiClO4. All the solid polymer electrolytes had sufficient thermal stability as confirmed by TGA and exhibited a single-phase behavior evidenced by DSC results. For these electrolytes, FT-IR spectra indicated the formation of polymer-ion complexes. The ac impedance spectra show that the conductivity of the electrolytes follow the Arrhenius behavior, and ionic conductivity is associated with both the charge migration of ions between coordination sites and transmission between aggregates, as confirmed by FT-IR and SEM. Alkyl quaternary ammonium salts in the polymer backbone are recognized as inherent plasticizers, which make the electrolytes exhibit liquid-like behavior. The plasticizing effect of PU-C8 and PU-C14 electrolytes are more effective than that of PU-C2 electrolyte. Maximum ionic conductivity at room temperature for PU-C8 electrolytes containing 50 wt% LiClO4 reached 1.1 × 10-4 S cm-1. This work provides a new research clue that alkyl quaternary ammonium salts could be used as inherent plasticizers and hence make the system behave like a liquid with high ionic conductivity, while preserving the dimensional stability of the solids.

  9. Lipopolythioureas: a new non-cationic system for gene transfer.

    PubMed

    Leblond, Jeanne; Mignet, Nathalie; Largeau, Céline; Spanedda, Maria-Vittoria; Seguin, Johanne; Scherman, Daniel; Herscovici, Jean

    2007-01-01

    A DNA-transfection protocol has been developed that makes use of thiourea non-cationic synthetic lipid, N-[1,3-bis(carbamothioylamino)propan-2-yl]-2-(dialkycarbamoylmethoxy)acetamide. It was found that these new compounds could be formulated without helper lipid and that the N-decanoyl and N-lauryl derivatives transfected B16 cells in the presence of serum with an efficiency at the same level as cationic lipids, under identical conditions. In vivo transfection using intratumoral injection was also investigated. It was found that compounds 18c and 19 showed an efficiency of the same magnitude as naked DNA and cationic lipid. PMID:17373770

  10. Pyridine radical cation and its fluorine substituted derivatives

    USGS Publications Warehouse

    Bondybey, V.E.; English, J.H.; Shiley, R.H.

    1982-01-01

    The spectra and relaxation of the pyridine cation and of several of its fluorinated derivatives are studied in low temperature Ne matrices. The ions are generated by direct photoionization of the parent compounds. Of the compounds studied, laser induced → and → fluorescence is observed only for the 2, 6‐difluoropyridine cation. The analysis of the spectrum indicates that the ion is planar both in the and states. The large variety in the spectroscopic and relaxation behavior of fluoropyridine radical cations is explained in terms of their electronic structure and of the differential shifts of the individual electronic states caused by the fluorine substitution.

  11. Increased Vascular permeability produced by human platelet granule cationic extract

    PubMed Central

    Nachman, Ralph L.; Weksler, Babette; Ferris, Barbara

    1970-01-01

    A cationic protein extract obtained from isolated human platelet granules increased vascular permeability in mouse and rabbit skin. The permeability-enhancing effect was not inhibited by soybean trypsin and pancreatic trypsin inhibitor, methylsergide maleate, carboxypeptidase B, and C[unk]1 inactivator. Permeability-enhancing activity was blocked by prior treatment of challenged animals with antihistamine. The nondializable relatively heat-stable cationic granule protein extract possessed potent mastocytolytic activity. The experiments described suggest that human platelets exert a permeability-enhancing effect by lysosomal release of cationic proteins which cause histamine release from adjacent tissue mast cells. Images PMID:4391559

  12. Electrostatic charge confinement using bulky tetraoctylammonium cation and four anions

    NASA Astrophysics Data System (ADS)

    Andreeva, Nadezhda A.; Chaban, Vitaly V.

    2016-04-01

    Thanks to large opposite electrostatic charges, cations and anions establish strong ionic bonds. However, applications of ionic systems - electrolytes, gas capture, solubilization, etc. - benefit from weaker non-covalent bonds. The common approaches are addition of cosolvents and delocalization of electron charge density via functionalization of ions. We report fine tuning of closest-approach distances, effective radii, and cation geometry by different anions using the semi-empirical molecular dynamics simulations. We found that long fatty acid chains employed in the tetraalkylammonium cation are largely inefficient and new substituents must be developed. The reported results foster progress of task-specific ionic liquids.

  13. Aryl sulfoxide radical cations. Generation, spectral properties, and theoretical calculations.

    PubMed

    Baciocchi, Enrico; Del Giacco, Tiziana; Gerini, Maria Francesca; Lanzalunga, Osvaldo

    2006-08-17

    Aromatic sulfoxide radical cations have been generated by pulse radiolysis and laser flash photolysis techniques. In water (pulse radiolysis) the radical cations showed an intense absorption band in the UV region (ca. 300 nm) and a broad less intense band in the visible region (from 500 to 1000 nm) whose position depends on the nature of the ring substituent. At very low pulse energy, the radical cations decayed by first-order kinetics, the decay rate increasing as the pH increases. It is suggested that the decay involves a nucleophilic attack of H(2)O or OH(-) (in basic solutions) to the positively charged sulfur atom to give the radical ArSO(OH)CH(3)(*). By sensitized [N-methylquinolinium tetrafluoborate (NMQ(+))] laser flash photolysis (LFP) the aromatic sulfoxide radical cations were generated in acetonitrile. In these experiments, however, only the band of the radical cation in the visible region could be observed, the UV band being covered by the UV absorption of NMQ(+). The lambda(max) values of the bands in the visible region resulted almost identical to those observed in water for the same radical cations. In the LFP experiments the sulfoxide radical cations decayed by second-order kinetics at a diffusion-controlled rate, and the decay is attributed to the back electron transfer between the radical cation and NMQ(*). DFT calculations were also carried out for a number of 4-X ring substituted (X = H, Me, Br, OMe, CN) aromatic sulfoxide radical cations (and their neutral parents). In all radical cations, the conformation with the S-O bond almost coplanar with the aromatic ring is the only one corresponding to the energy minimum. The maximum of energy corresponds to the conformation where the S-O bond is perpendicular to the aromatic ring. The rotational energy barriers are not very high, ranging from 3.9 to 6.9 kcal/mol. In all radical cations, the major fraction of charge and spin density is localized on the SOMe group. However, a substantial delocalization

  14. Radical cations of sulfides and disulfides: An ESR study

    SciTech Connect

    Bonazzola, L.; Michaut, J.P.; Roncin, J.

    1985-09-15

    Exposure of dilute solutions of dimethylsulfide, methanethiol, tetrahydrothiophene, terbutyl and diterbutyl-sulfides, dimethyl-disulfide, and diterbutyldisulfide, in freon at 77 K to /sup 60/Co ..gamma.. rays gave the corresponding cations. From the reported ESR spectra, g tensors were obtained. It was found that both sulfide and disulfide cations exhibit the same g tensor: (g/sub max/ = 2.034 +- 0.002, g/sub int/ = 2.017 +- 0.001, g/sub min/ = 2.001 +- 0.005). From this result it has been shown that the disulfide cation is planar. This finding was supported by fully optimized geometry ab initio calculations.

  15. Absorbable microparticulate cation exchanger for immunotherapeutic delivery.

    PubMed

    Shalaby, Waleed S W; Yeh, Heidi; Woo, Edward; Corbett, Joel T; Gray, Heidi; June, Carl H; Shalaby, Shalaby W

    2004-05-15

    An absorbable microparticulate cation exchanger was synthesized as a versatile carrier for biologically active proteins. In this work, acid-terminated polyglycolide (or polyglycolic acid) microparticulates (PG-MP) were surface modified for either sustained release of cytokines or as a platform for immunomodulation. The intended goal was to achieve in situ recruitment/maturation of dendritic cells and activation of T cells for tumor immunotherapy. PG-MP were prepared with a volume weighted mean diameter of 7.02 micro (range: 2.09-14.58 micro). Accessible carboxylic acid groups were determined to be 0.3 mmol/g with a corresponding zeta potential of -21.87 mV in phosphate-buffered saline. Under low magnification, scanning electron microscopy (SEM) revealed a highly textured surface due to processing from repetitive jet milling. However, a moderately porous architecture was noted at higher magnification. Electron spectroscopy for chemical analysis was used to characterize the PG-MP surface before and after adsorption of human granulocyte-macrophage colony stimulating factor (GM-CSF). Adsorption of GM-CSF on PG-MP (PG-GMCSF) resulted in a modest increase in the surface atomic concentration of nitrogen (0.97%). Pretreating the surface with poly-L-lysine (PG/Lys-GMCSF) prior to adding GM-CSF produced a nearly threefold increase in the surface nitrogen concentration (4.20% compared to 1.47%). This manipulation not only increased loading content, but also prolonged the release of GM-CSF released from 6 days to 26 days. ESCA on the post-release PG-MP samples (PG-GMCSF and PG/Lys-GMCSF) revealed a similar residual surface nitrogen concentration (2.26% vs. 2.35%). The observation was consistent with irreversibly adsorbed GM-CSF. It is postulated that irreversibly bound GM-CSF is released over time as a function of microparticulate degradation. Biological activity of released GM-CSF was confirmed by the proliferation of a GM-CSF-dependent cell line (TF-1) in the presence of

  16. Dissociative Recombination Dynamics of the Ozone Cation

    SciTech Connect

    Zhaunerchyk, Vitali; Geppert, W.; sterdahl, F.; Larsson, Mats; Thomas, R. D.; Bahati Musafiri, Eric; Bannister, Mark E; Fogle, Mark R.; Vane, C Randy

    2008-02-01

    The dissociative recombination of the ozone cation has been studied at the heavy-ion storage ring CRYRING. The total cross section and branching fractions have been measured. The cross section from {approx}0eV to 0.2 eV follows a nearly E{sup -1} dependence, which was theoretically predicted to be a characteristic of the direct dissociative recombination mechanism. The thermal rate coefficient has been deduced from the cross section to be 7.37x10{sup -7}(T/300){sup -0.55}cm{sup 3}s{sup -1}. The branching fraction analysis carried out at {approx}0eV interaction energy has shown a strong propensity (94%) to dissociate through the three-body channel. Due to the overwhelming dominance of this channel it has been investigated in more detail. Of the six energetically available three-body pathways only three are significantly populated, such that the production of O(S1) is highly unfavored and all atomic oxygen fragments are predominantly formed in P3 and D1 states. Analysis of the breakup geometries has been performed by means of the Dalitz plot. It is observed that the molecules dissociating through the O(P3)+O(P3)+O(P3) and O(P3)+O(P3)+O(D1) channels have an open linear geometry where the cleavage of two valence bonds occurs preferentially in unison, while the O(P3)+O(D1)+O(D1) breakup might proceed partly through a sequential mechanism.

  17. Anaerobic toxicity of cationic silver nanoparticles.

    PubMed

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

    2016-07-01

    The microbial toxicity of silver nanoparticles (AgNPs) stabilized with different capping agents was compared to that of Ag(+) under anaerobic conditions. Three AgNPs were investigated: (1) negatively charged citrate-coated AgNPs (citrate-AgNPs), (2) minimally charged polyvinylpyrrolidone coated AgNPs (PVP-AgNPs) and (3) positively charged branched polyethyleneimine coated AgNPs (BPEI-AgNPs). The AgNPs investigated in this experiment were similar in size (10-15nm), spherical in shape, but varied in surface charge which ranged from highly negative to highly positive. While, at AgNPs concentrations lower than 5mgL(-1), the anaerobic decomposition process was not influenced by the presence of the nanoparticles, there was an observed impact on the diversity of the microbial community. At elevated concentrations (100mgL(-1) as silver), only the cationic BPEI-AgNPs demonstrated toxicity similar in magnitude to that of Ag(+). Both citrate and PVP-AgNPs did not exhibit toxicity at the 100mgL(-1) as measured by biogas evolution. These findings further indicate the varying modes of action for nanoparticle toxicity and represent one of the few studies that evaluate end-of-life management concerns with regards to the increasing use of nanomaterials in our everyday life. These findings also highlight some of the concerns with a one size fits all approach to the evaluation of environmental health and safety concerns associated with the use of nanoparticles. PMID:27016684

  18. Novel cationic polyelectrolyte coatings for capillary electrophoresis.

    PubMed

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

    2016-01-01

    The use of bare fused silica capillary in CE can sometimes be inconvenient due to undesirable effects including adsorption of sample or instability of the EOF. This can often be avoided by coating the inner surface of the capillary. In this work, we present and characterize two novel polyelectrolyte coatings (PECs) poly(2-(methacryloyloxy)ethyl trimethylammonium iodide) (PMOTAI) and poly(3-methyl-1-(4-vinylbenzyl)-imidazolium chloride) (PIL-1) for CE. The coated capillaries were studied using a series of aqueous buffers of varying pH, ionic strength, and composition. Our results show that the investigated polyelectrolytes are usable as semi-permanent (physically adsorbed) coatings with at least five runs stability before a short coating regeneration is necessary. Both PECs showed a considerably decreased stability at pH 11.0. The EOF was higher using Good's buffers than with sodium phosphate buffer at the same pH and ionic strength. The thickness of the PEC layers studied by quartz crystal microbalance was 0.83 and 0.52 nm for PMOTAI and PIL-1, respectively. The hydrophobicity of the PEC layers was determined by analysis of a homologous series of alkyl benzoates and expressed as the distribution constants. Our result demonstrates that both PECs had comparable hydrophobicity, which enabled separation of compounds with log Po/w > 2. The ability to separate cationic drugs was shown with β-blockers, compounds often misused in doping. Both coatings were also able to separate hydrolysis products of the ionic liquid 1,5-diazabicyclo[4.3.0]non-5-ene acetate at highly acidic conditions, where bare fused silica capillaries failed to accomplish the separation. PMID:26464098

  19. Recognition of metal cations by biological systems.

    PubMed

    Truter, M R

    1975-11-01

    Recognition of metal cations by biological systems can be compared with the geochemical criteria for isomorphous replacement. Biological systems are more highly selective and much more rapid. Methods of maintaining an optimum concentration, including storage and transfer for the essential trace elements, copper and iron, used in some organisms are in part reproducible by coordination chemists while other features have not been reporduced in models. Poisoning can result from a foreign metal taking part in a reaction irreversibly so that the recognition site or molecule is not released. For major nutrients, sodium, potassium, magnesium and calcium, there are similarities to the trace metals in selective uptake but differences qualitatively and quantitatively in biological activity. Compounds selective for potassium replace all the solvation sphere with a symmetrical arrangement of oxygen atoms; those selective for sodium give an asymmetrical environment with retention of a solvent molecule. Experiments with naturally occurring antibiotics and synthetic model compounds have shown that flexibility is an important feature of selectivity and that for transfer or carrier properties there is an optimum (as opposed to a maximum) metal-ligand stability constant. Thallium is taken up instead of potassium and will activate some enzymes; it is suggested that the poisonous characteristics arise because the thallium ion may bind more strongly than potassium to part of a site and then fail to bind additional atoms as required for the biological activity. Criteria for the design of selective complexing agents are given with indications of those which might transfer more than one metal at once. PMID:1815

  20. Effects of nonframework metal cations and phonon scattering mechanisms on the thermal transport properties of polycrystalline zeolite LTA films

    NASA Astrophysics Data System (ADS)

    Greenstein, Abraham; Hudiono, Yeny; Graham, Samuel; Nair, Sankar

    2010-03-01

    We present a systematic study to investigate the effects of nonframework cations and the role of phonon scattering mechanisms on the thermal transport properties of zeolite LTA, via experiment and semiempirical lattice dynamics calculations. Our study is motivated by the increasing interest in accurate measurements and mechanistic understanding of the thermal transport properties of zeolite materials. The presence of a nanostructured pore network, extra-framework cations, and tunable framework structure and composition confer interesting thermophysical properties to these materials, making them a good model system to investigate thermal transport in complex materials. Continuous films of zeolite LTA with different nonframework cations (Na+, K+, and Ca+2) were synthesized and characterized. The thermal conductivity was measured using the three-omega method over a wide range of temperature (150-450 K). These are the first thermal conductivity measurements performed on bulk LTA, so they are more accurate than previous measurements, which involved the use of compacted zeolite powders. Our data showed significant dependence of the thermal conductivity on the extra-framework cations as well the temperature. The thermal conductivities of the zeolite LTA samples were modeled with the relaxation time approximation to the Boltzmann transport equation. The full phonon spectra for each type of LTA zeolite were calculated and used in conjunction with semiempirical relaxation time expressions to calculate the thermal conductivity. The results both validated, and suggested the limitations of, this modeling approach. Optical phonons dominated the thermal conductivity and boundarylike scattering was found to be the strongest phonon scattering mechanism, as also observed in MFI zeolite.

  1. Cation-Cation Interactions in [(UO2)2(OH)n](4-n) Complexes

    SciTech Connect

    Odoh, Samuel O.; Govind, Niranjan; Schreckenbach, Georg; De Jong, Wibe A.

    2013-10-07

    The structures and bonding of gas-phase [(UO2)2(OH)n]4-n (n=2-6) complexes have been studied using density functional theory (DFT), MP2 and CCSD(T) methods with particular emphasis on ground state structures featuring cation-cation interactions (CCIs) between the uranyl groups. An interesting trend is observed in the stabilities of members of this series of complexes. The structures of [(UO2)2(OH)2]2+, [(UO2)2(OH)4] and [(UO2)2(OH)6]2- featuring CCIs are found at higher energies (by 3-20 kcal/mol) in comparison to their conventional μ2-dihydroxo structures. In contrast, the CCI structures of [(UO2)2(OH)3]+ and [(UO2)2(OH)5]- are respectively almost degenerate with and lower in energy than the structures with the μ2-dihydroxo format. The origin of this trend lies in the ‘symmetry’-based need to balance the coordination numbers and effective atomic charges of each uranium center. The calculated IR vibrational frequencies provide signature probes that can be used in differentiating the lowenergy structures and in experimentally confirming the existence of the structures featuring CCIs. Analysis of the bonding in the structures of [(UO2)2(OH)3]+ and [(UO2)2(OH)5]- shows that the CCIs and bridging hydroxo between the dioxo-uranium units are mainly electrostatic in nature.

  2. Effects of biofouling on ion transport through cation exchange membranes and microbial fuel cell performance.

    PubMed

    Choi, Mi-Jin; Chae, Kyu-Jung; Ajayi, Folusho F; Kim, Kyoung-Yeol; Yu, Hye-Weon; Kim, Chang-Won; Kim, In S

    2011-01-01

    This study examines the effects of biofouling on the electrochemical properties of cation exchange membranes (CEMs), such as membrane electrical resistance (MER), specific proton conductivity (SC), and ion transport number (t(+)), in addition to on microbial fuel cell (MFC) performance. CEM biofouling using a 15.5 ± 4.6 μm biofilm was found to slightly increase the MER from 15.65 Ω cm(2) (fresh Nafion) to 19.1 Ω cm(2), whereas an increase of almost two times was achieved when the electrolyte was changed from deionized water to an anolyte containing a high cation concentration supporting bacterial growth. The simple physical cleaning of CEMs had little effect on the Coulombic efficiency (CE), whereas replacing a biofouled CEM with new one resulted in considerable increase of up to 59.3%, compared to 45.1% for a biofouled membrane. These results clearly suggest the internal resistance increase of MFC was mainly caused by the sulfonate functional groups of CEM being occupied with cations contained in the anolyte, rather than biofouling itself. PMID:20659795

  3. Polyamines control of cation transport across plant membranes: implications for ion homeostasis and abiotic stress signaling

    PubMed Central

    Pottosin, Igor; Shabala, Sergey

    2014-01-01

    Polyamines are unique polycationic metabolites, controlling a variety of vital functions in plants, including growth and stress responses. Over the last two decades a bulk of data was accumulated providing explicit evidence that polyamines play an essential role in regulating plant membrane transport. The most straightforward example is a blockage of the two major vacuolar cation channels, namely slow (SV) and fast (FV) activating ones, by the micromolar concentrations of polyamines. This effect is direct and fully reversible, with a potency descending in a sequence Spm4+ > Spd3+ > Put2+. On the contrary, effects of polyamines on the plasma membrane (PM) cation and K+-selective channels are hardly dependent on polyamine species, display a relatively low affinity, and are likely to be indirect. Polyamines also affect vacuolar and PM H+ pumps and Ca2+ pump of the PM. On the other hand, catabolization of polyamines generates H2O2 and other reactive oxygen species (ROS), including hydroxyl radicals. Export of polyamines to the apoplast and their oxidation there by available amine oxidases results in the induction of a novel ion conductance and confers Ca2+ influx across the PM. This mechanism, initially established for plant responses to pathogen attack (including a hypersensitive response), has been recently shown to mediate plant responses to a variety of abiotic stresses. In this review we summarize the effects of polyamines and their catabolites on cation transport in plants and discuss the implications of these effects for ion homeostasis, signaling, and plant adaptive responses to environment. PMID:24795739

  4. Solution Versus Gas-Phase Modification of Peptide Cations with NHS-Ester Reagents

    NASA Astrophysics Data System (ADS)

    Mentinova, Marija; Barefoot, Nathan Z.; McLuckey, Scott A.

    2012-02-01

    A comparison between solution and gas phase modification of primary amine sites in model peptide cations with N-hydroxysuccinimide (NHS) ester reagents is presented. In all peptides, the site of modification in solution was directed to the N-terminus by conducting reactions at pH = 5, whereas for the same peptides, a lysine residue was preferentially modified in the gas phase. The difference in pKa values of the N-terminus and ɛ-amino group of the lysine allows for a degree of control over sites of protonation of the peptides in aqueous solution. With removal of the dielectric and multiple charging of the peptide ions in the gas phase, the accommodation of excess charge can affect the preferred sites of reaction. Interaction of the lone pair of the primary nitrogen with a proton reduces its nucleophilicity and, as a result, its reactivity towards NHS-esters. While no evidence for reaction of the N-terminus with sulfo-NHS-acetate was noted in the model peptide cations, a charge inversion experiment using bis[sulfosuccinimidyl] suberate, a cross-linking reagent with two sulfo-NHS-ester functionalities, showed modification of the N-terminus. Hence, an unprotonated N-terminus can serve as a nucleophile to displace NHS, which suggests that its lack of reactivity with the peptide cations is likely due to the participation of the N-terminus in solvating excess charge.

  5. Structure-Property Relationships in Hydroxide-Exchange Membranes with Cation Strings and High Ion-Exchange Capacity.

    PubMed

    Wang, Junhua; Gu, Shuang; Xiong, Ruichang; Zhang, Bingzi; Xu, Bingjun; Yan, Yushan

    2015-12-21

    A series of poly(2,4-dimethyl-1,4-phenylene oxide) hydroxide-exchange membranes (HEMs) with cation strings containing a well-defined number of cations (CS-n) and similar, high ion-exchange capacities are synthesized to investigate the effect of cation distribution on key HEM properties. As the number of cations on each string grows, the size of the ionic clusters increases from 10 to 55 nm. Well-connected ion pathways and a hydrophobic framework are observed for n≥4. The enhanced phase segregation increases the hydroxide conductivity from CS-1 to CS-6 (30 to 65 mS cm(-1) ) and suppresses the water uptake (from 143 % to 62 %). Moreover, molar hydroxide conductivities for CS-n membranes show two distinctive stages as n increases: ∼23 S cm(2)  mol(-1) for n≤3; and ∼34 cm(2)  mol(-1) for n≥4. PMID:26630241

  6. Reduction by monovalent zinc, cadmium, and nickel cations

    NASA Technical Reports Server (NTRS)

    Meyerstein, D.; Mulac, W. A.

    1969-01-01

    Understanding of chemical properties of monovalent transition metal cations in aqueous solutions was obtained by a study of kinetics of reduction of different inorganic substrates by zinc, cadmium, and nickel.

  7. Investigation of Fragmentation of Tryptophan Nitrogen Radical Cation

    NASA Astrophysics Data System (ADS)

    Piatkivskyi, Andrii; Happ, Marshall; Lau, Justin Kai-Chi; Siu, K. W. Michael; Hopkinson, Alan C.; Ryzhov, Victor

    2015-08-01

    This work describes investigation of the fragmentation mechanism of tryptophan N-indolyl radical cation, H3N+-TrpN• ( m/ z 204) studied via DFT calculations and several gas-phase experimental techniques. The main fragment ion at m/ z 131, shown to be a mixture of up to four isomers including 3-methylindole (3MI) π-radical cation, was found to undergo further loss of an H atom to yield one of the two isomeric m/ z 130 ions. 3-Methylindole radical cation generated independently (via CID of [CuII(terpy)3MI]•2+) displayed gas-phase reactivity partially similar to that of the m/ z 131 fragment, further confirming our proposed mechanism. CID of deuterated tryptophan N-indolyl radical cation ( m/ z 208) suggested that up to six H atoms are involved in the pathway to formation of the m/ z 131 ion, consistent with hydrogen atom scrambling during CID of protonated Trp.

  8. Study on cationic photopolymerization reaction of epoxy polysiloxane

    NASA Astrophysics Data System (ADS)

    Sun, F.; Jiang, S. L.; Liu, J.

    2007-11-01

    The effects of epoxy monomers, concentration of photoinitiator and radical photoinitiators on the photosensitive properties of cationic phopolymerization system with a novel epoxy polysiloxane oligomer (CEPS) were investigated via a gel yield method. The results showed that among the tested epoxy monomers, the reactivity of ERL-4221 with cycloaliphatic epoxy groups was the highest. The optimum concentration of diaryldiodonium salt (SR-1012) was determined as 4-5 wt.%. Increasing the amounts of ERL-4221 in the CEPS cationic photopolymerization system, UV-curing rate increased. Radical photoinitiators with ArC dbnd O structure possessed sensitization capacity to the cationic photoinitiator SR-1012. The photosensitivity of the CEPS system could be up to 165 mJ/cm 2. Adding a small amount of IPA and BP could greatly improve the photosensitivity of CEPS cationic photosensitive system. The optimal quantity of isopropanol added to the system was not more than 2 wt.%.

  9. Infrared spectroscopy of mass-selected metal carbonyl cations

    NASA Astrophysics Data System (ADS)

    Ricks, A. M.; Reed, Z. E.; Duncan, M. A.

    2011-04-01

    Metal carbonyl cations of the form M(CO)n+ are produced in a molecular beam by laser vaporization in a pulsed nozzle source. These ions, and their corresponding rare gas atom "tagged" analogs, M(CO)n(RG)m+, are studied with mass-selected infrared photodissociation spectroscopy in the carbonyl stretching region and with density functional theory computations. The number of infrared-active bands, their frequency positions, and their relative intensities provide distinctive patterns allowing determination of the geometries and electronic structures of these complexes. Cobalt penta carbonyl and manganese hexacarbonyl cations are compared to isoelectronic iron pentacarbonyl and chromium hexacarbonyl neutrals. Gold and copper provide examples of "non-classical" carbonyls. Seven-coordinate carbonyls are explored for the vanadium group metal cations (V +, Nb + and Ta +), while uranium cations provide an example of an eight-coordinate carbonyl.

  10. Cationic RAFT polymerization using ppm concentrations of organic acid.

    PubMed

    Uchiyama, Mineto; Satoh, Kotaro; Kamigaito, Masami

    2015-02-01

    A metal-free, cationic, reversible addition-fragmentation chain-transfer (RAFT) polymerization was proposed and realized. A series of thiocarbonylthio compounds were used in the presence of a small amount of triflic acid for isobutyl vinyl ether to give polymers with controlled molecular weight of up to 1×10(5) and narrow molecular-weight distributions (Mw /Mn <1.1). This "living" or controlled cationic polymerization is applicable to various electron-rich monomers including vinyl ethers, p-methoxystyrene, and even p-hydroxystyrene that possesses an unprotected phenol group. A transformation from cationic to radical RAFT polymerization enables the synthesis of block copolymers between cationically and radically polymerizable monomers, such as vinyl ether and vinyl acetate or methyl acrylate. PMID:25511364

  11. DFT study on the cycloreversion of thietane radical cations.

    PubMed

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

    2011-06-01

    The molecular mechanism of the cycloreversion (CR) of thietane radical cations has been analyzed in detail at the UB3LYP/6-31G* level of theory. Results have shown that the process takes place via a stepwise mechanism leading to alkenes and thiobenzophenone; alternatively, formal [4+2] cycloadducts are obtained. Thus, the CR of radical cations 1a,b(•+) is initiated by C2-C3 bond breaking, giving common intermediates INa,b. At this stage, two reaction pathways are feasible involving ion molecule complexes IMCa,b (i) or radical cations 4a,b(•+) (ii). Calculations support that 1a(•+) follows reaction pathway ii (leading to the formal [4+2] cycloadducts 5a). By contrast, 1b(•+) follows pathway i, leading to trans-stilbene radical cation (2b(•+)) and thiobenzophenone. PMID:21561127

  12. α-Cationic Arsines: Synthesis, Structure, Reactivity, and Applications.

    PubMed

    Dube, Jonathan W; Zheng, Yiying; Thiel, Walter; Alcarazo, Manuel

    2016-06-01

    A series of structurally differentiated cationic arsines containing imidazolium, cyclopropenium, formamidinium, and pyridinium substituents have been synthesized through short and scalable routes. Evaluation of the donor properties of these compounds by IR spectroscopy and DFT calculations reveals similar σ-electron-releasing abilities for all of them; however, their π-acceptor properties are strongly influenced by the nature of the positively charged group. We describe the coordination chemistry of the newly prepared α-cationic arsines toward different metal centers and their reactivity in the presence of strong oxidants to afford cationic As(V) species. Their unique electronic properties have been exploited in Pt(II) catalysis to develop a new catalyst with remarkable activity in the cycloisomerization of enynes to trisubstituted cyclopropanes. To the best of our knowledge, this is the first report on the use of α-cationic arsine ligands in catalysis. PMID:27214007

  13. The Ziegler—Natta olefin insertion reaction for cationic metals

    NASA Astrophysics Data System (ADS)

    Jensen, Vidar R.; Siegban, Per E. M.

    1993-09-01

    The catalytic Ziegler—Natta polymerization reaction has been studied for a set of metal cations, in order to identify the role of the positive charge on this process. Geometry optimizations have been performed for the reactant metal—methyl systems, the π-coordinated olefin systems, the transition states for the olefin insertion and finally for the product metal—propyl systems. All valence electrons are correlated. The cations selected for this study are the transition metals Zr + and Ti +, the non-transition metals Be +, Mg +, Al + and finally also Si +. The transition metal cations are found to have very low barriers for the insertion, but the lowest barrier is actually found for Be +. The results are discussed in terms of the ionization energies and the accessibility to valence p and d orbitals. Comparisons are made to previous theoretical work on cationic model systems.

  14. Role of nonselective cation channels in spontaneous and protein kinase A-stimulated calcium signaling in pituitary cells.

    PubMed

    Tomić, Melanija; Kucka, Marek; Kretschmannova, Karla; Li, Shuo; Nesterova, Maria; Stratakis, Constantine A; Stojilkovic, Stanko S

    2011-08-01

    Several receptors linked to the adenylyl cyclase signaling pathway stimulate electrical activity and calcium influx in endocrine pituitary cells, and a role for an unidentified sodium-conducting channel in this process has been proposed. Here we show that forskolin dose-dependently increases cAMP production and facilitates calcium influx in about 30% of rat and mouse pituitary cells at its maximal concentration. The stimulatory effect of forskolin on calcium influx was lost in cells with inhibited PKA (cAMP-dependent protein kinase) and in cells that were haploinsufficient for the main PKA regulatory subunit but was preserved in cells that were also haploinsufficient for the main PKA catalytic subunit. Spontaneous and forskolin-stimulated calcium influx was present in cells with inhibited voltage-gated sodium and hyperpolarization-activated cation channels but not in cells bathed in medium, in which sodium was replaced with organic cations. Consistent with the role of sodium-conducting nonselective cation channels in PKA-stimulated Ca(2+) influx, cAMP induced a slowly developing current with a reversal potential of about 0 mV. Two TRP (transient receptor potential) channel blockers, SKF96365 and 2-APB, as well as flufenamic acid, an inhibitor of nonselective cation channels, also inhibited spontaneous and forskolin-stimulated electrical activity and calcium influx. Quantitative RT-PCR analysis indicated the expression of mRNA transcripts for TRPC1 > TRPC6 > TRPC4 > TRPC5 > TRPC3 in rat pituitary cells. These experiments suggest that in pituitary cells constitutively active cation channels are stimulated further by PKA and contribute to calcium signaling indirectly by controlling the pacemaking depolarization in a sodium-dependent manner and directly by conducting calcium. PMID:21586701

  15. Electrical Properties and Cation Valences in the

    NASA Astrophysics Data System (ADS)

    Sehlin, Scott Richard

    The electrical properties of the (La,Ca)(Cr,Co)O _3 system were studied as a function of temperature and composition to determine the mechanisms of charge transport and charge carrier formation. The results of electrical conductivity measurements were found to be consistent with the small polaron conduction mechanism. A room temperature electrical conductivity minimum as a function of Cr content was observed for small Cr content in rm La_{1-x}Ca_{x}(Cr,Co)O _3 for x = 0.1 and for x = 0.2. This minimum was attributed to the trapping of p-type small polarons at energetically lower Cr sites. The results of Seebeck coefficient measurements for the (La,Ca)(Cr,Co)O _3 system were interpreted using the mechanism of thermally activated charge disproportionation among Co ions. To further investigate the plausibility of the assumptions of thermally activated charge disproportionation and of a small polaron conduction mechanism, a model incorporating those assumptions was developed for the electrical conductivity and Seebeck coefficient of (La,Ca)CoO_3 compositions. The temperature dependence of the electrical conductivity and Seebeck coefficient of the compositions studied was successfully modelled only when the free energy of disproportionation was modified to include coulomb screening-like interactions between charge carriers. These screening-like interactions account for the deviations from the dilute limit that arise due to the high carrier concentrations produced through thermally activated charge disproportionation. The mechanism of screening utilized in the model is also consistent with the experimentally observed trend that the free energy of disproportionation decreases with increasing acceptor (Ca) content for (La,Ca)CoO _3.

  16. Cationically polymerizable monomers derived from renewable sources. Final report

    SciTech Connect

    1995-09-01

    Objective is to use products from plant sources as monomers for direct production of polymers for plastic applications. (Epoxidized triglycerides as renewable monomers in photoinitiated cationic polymerization.) High-volume American agricultural products such as soybean, cotton or linseed oils or forestry products such as lignin and cellulose derived chemicals were targeted for use either directly or with slight modification for producing the plastics. Cationic photopolymerization will be used.

  17. Characterization of the Azirinyl Cation and Its Isomers.

    PubMed

    Kokkila Schumacher, Sara I L; Bera, Partha P; Lee, Timothy J

    2016-03-01

    The azirinyl cation (C2H2N(+)) and its geometrical isomers could be present in the interstellar medium. The C2H2N(+) isomers are, however, difficult to identify in interstellar chemistry because of the lack of high-resolution spectroscopic data from laboratory experiments. Ab initio quantum chemical methods were used to characterize the structures, relative energies, and spectroscopic and physical properties of the low energy isomers of the azirinyl cation. We have employed second-order Møller-Plesset perturbation theory (MP2), second-order Z-averaged perturbation theory (ZAPT2), and coupled cluster theory with singles and doubles with perturbative triples CCSD(T) methods along with large correlation consistent basis sets such as cc-pVTZ, cc-pCVTZ, cc-pVQZ, cc-pCVQZ, and cc-pV5Z. Harmonic vibrational frequencies, dipole moments, rotational constants, and proton affinities for the lowest energy isomers were calculated using the CCSD(T) method. Azirinyl cation, a cyclic isomer, is lowest in energy at all levels of theory employed. Azirinyl cation is followed by the cyanomethyl cation (H2CCN)(+), isocyanomethyl cation (H2CNC)(+), and a quasilinear HCCNH(+) cation, which are 13.8, 17.3, and 21.5 kcal mol(-1) above the cyclic isomer, respectively, at the CCSD(T)/cc-pV5Z level of theory. The lowest three isomers all have C2v symmetry and (1)A1 ground electronic states. The quasilinear HCCNH(+) cation has a Cs symmetry planar structure, and a (3)A″ electronic ground state, unlike what some previous work suggested. PMID:26840658

  18. Mercury release from deforested soils triggered by base cation enrichment.

    PubMed

    Farella, N; Lucotte, M; Davidson, R; Daigle, S

    2006-09-01

    The Brazilian Amazon has experienced considerable colonization in the last few decades. Family agriculture based on slash-and-burn enables millions of people to live in that region. However, the poor nutrient content of most Amazonian soils requires cation-rich ashes from the burning of the vegetation biomass for cultivation to be successful, which leads to forest ecosystem degradation, soil erosion and mercury contamination. While recent studies have suggested that mercury present in soils was transferred towards rivers upon deforestation, little is known about the dynamics between agricultural land-use and mercury leaching. In this context, the present study proposes an explanation that illustrates how agricultural land-use triggers mercury loss from soils. This explanation lies in the competition between base cations and mercury in soils which are characterized by a low adsorption capacity. Since these soils are naturally very poor in base cations, the burning of the forest biomass suddenly brings high quantities of base cations to soils, destabilizing the previous equilibrium amongst cations. Base cation enrichment triggers mobility in soil cations, rapidly dislocating mercury atoms. This conclusion comes from principal component analyses illustrating that agricultural land-use was associated with base cation enrichment and mercury depletion. The overall conclusions highlight a pernicious cycle: while soil nutrient enrichment actually occurs through biomass burning, although on a temporary basis, there is a loss in Hg content, which is leached to rivers, entering the aquatic chain, and posing a potential health threat to local populations. Data presented here reflects three decades of deforestation activities, but little is known about the long-term impact of such a disequilibrium. These findings may have repercussions on our understanding of the complex dynamics of deforestation and agriculture worldwide. PMID:16781764

  19. Cloning and first functional characterization of a plant cyclic nucleotide-gated cation channel

    SciTech Connect

    Leng, Q.; Mercier, R.W.; Yao, W.; Berkowitz, G.A.

    1999-11-01

    Cyclic nucleotide-gated (cng) non-selective cation channels have been cloned from a number of animal systems. These channels are characterized by direct gating upon cAMO or cGMO binding to the intracellular portion of the channel protein, which leads to an increase in channel conductance. Animal cng channels are involved in signal transduction systems; they translate stimulus-induced changes in cytosolic cyclic nucleotide into altered cell membrane potential and/or cation flux as part of a signal cascade pathway. Putative plant homologs of animal cng channels have been identified. However, functional characterization (i.e., demonstration of cyclic-nucleotide-dependent ion currents) of a plant cng channel has not yet been accomplished. The authors report the cloning and first functional characterization of a plant member of this family of ion channels. The Arabidopsis cDNA AtCNGC2 encodes a polypeptide with deduced homology to the {alpha}-subunit of animal channels, and facilitates cyclic nucleotide-dependent cation currents upon expression in a number of heterologous systems. AtCNGC2 expression in a yeast mutant lacking a low-affinity K{sup +} uptake system complements growth inhibition only when lipophilic nucleotides are present in the culture medium. Voltage clamp analysis indicates that Xenopus lawvis oocytes injected with AtCNGC2 cRNA demonstrate cyclic-nucleotide-dependent, inward-rectifying K{sup +} currents. Human embryonic kidney cells (HEK293) transfected with AtCNGC2 cDNA demonstrate increased permeability to Ca{sup 2+} only in the presence of lipophilic cyclic nucleotides. The evidence presented here supports the functional classification of AtCNGC2 as a cyclic-nucleotide-gated cation channel, and presents the first direct evidence identifying a plant member of this ion channel family.

  20. Changes in the Vibrational Spectra of Zeolites Due to Sorption of Heavy Metal Cations

    NASA Astrophysics Data System (ADS)

    Król, M.; Mozgawa, W.; Barczyk, K.; Bajda, T.; Kozanecki, M.

    2013-11-01

    This work presents the results of spectroscopic (MIR and Raman) studies of zeolite structures after immobilization of heavy metal cations from aqueous solutions. The sorption of Ag+, Cu2+, Cd2+, Pb2+, Zn2+, and Cr3+ ions has been conducted on zeolites belonging to different structural groups, i.e., sodium forms of natural chabazite, mordenite, ferrierite, and clinoptilolite, as well as on synthetic zeolite Y. Systematic changes in intensities and positions of the bands corresponding to the characteristic ring vibrations have been observed in the measured spectra. The most visible changes are observed in the FT-IR spectra of the samples in the range of 850-450 cm-1, and in the Raman spectra in the range of 600-250 cm-1. Depending on the zeolite structure, the bands, which can be regarded as a kind of indicator of ion exchange, were indentifi ed. For example, in the case of IR spectra, these bands are at 766, 703, 648, 578, and 506 cm-1 for zeolite Y, at 733 and 560 cm-1 for mordenite, at 675 cm-1 for clinoptilolite, etc. The degree of changes depends on both the type of cation and its concentration in the initial solution. This is connected with the way of binding of metal ions to the zeolite aluminosilicate framework, i.e., a proportion of the ion exchange and chemisorption in the process. Cations mainly undergoing ion exchange, such as Cd2+ or Pb2+, have the greatest impact on the character of the spectra. On the other hand, Cr3+ ions practically do not modify the spectra of zeolites. Results of IR and Raman spectroscopic studies have been compared with those obtained by atomic absorption spectroscopy (AAS), from which the proportion of ion exchange to chemisorption in the process and the effective cation exchange capacity of the individual samples have been estimated.

  1. Structural effects of anions and cations on the aggregation behavior of ionic liquids in aqueous solutions.

    PubMed

    Wang, Huiyong; Wang, Jianji; Zhang, Shibiao; Xuan, Xiaopeng

    2008-12-25

    The formation of ionic liquids aggregates in aqueous solution is of great importance to the future applications of ionic liquids. In this work, aggregation behavior of 1-alkyl-3-methylimidazolium salts [C8mim]X (X = Cl, Br, [NO3], [CH3COO], [CF3COO], [CF3SO3], and [ClO4]), 1-octyl-4-methylpyridinium bromide (4m-[C8pyr]Br), and 1-methyl-1-octylpyrrolidinium ([C8mpyrr]Br) has been investigated in aqueous solutions by conductivity, volume, fluorescence, dynamic light scattering, and transmission electron microscopy. The critical aggregation concentration (CAC), ionization degree of the aggregates alpha, the standard Gibbs energy of aggregation deltaG(m)degrees, the average aggregation number N, the apparent molar volumes at critical aggregation concentration V(phi,CAC), the apparent molar volumes in aggregation phase V(phi)mic, and the change of the apparent molar volumes upon aggregation deltaV(phi,m), have been derived from the experimental data for these ionic liquids. It is found that both nature of the anions and ring type of the cations significantly affect the aggregation in aqueous solution. The anionic effect basically follows the Hofmeister series, and the ability of anionic hydration is predominant for the aggregation behavior of the ionic liquids. Hydrophobicity and steric hindrance of the cations as well as binding strength of the cations with the anions are suggested to play important roles in the aggregation of [C8mim]Br, 4m-[C8pyr]Br, and [C8mpyrr]Br. The investigated ILs were found to form spherical aggregates. Structures of anions and cations have very weak effects on the morphology, but they do affect the aggregate sizes. PMID:19367863

  2. Cation binding at the node of Ranvier: II. Redistribution of binding sites during electrical stimulation.

    PubMed

    Zagoren, J C; Arezzo, J C

    1982-06-17

    The nodal and paranodal areas of mature myelinated axons are known to bind cations. To examine whether the cation binding substance may play a role in saltatory conduction, a combined electrophysiological and histochemical study was undertaken. The sciatic nerve of anesthetized or unanesthetized adult C57B1 mice was exposed and not stimulated (control) or stimulated with constant square-wave pulses at one of the following rates: 10/sec, 30/sec, 100/sec or 500/sec. Phosphate-buffered 2.5% glutaraldehyde was either dropped onto the nerve during stimulation until cessation of the compound action potential or the nerve was fixed after discontinuing stimulation. The nerve was excised and processed for the histochemical reaction of copper sulfate/potassium ferrocyanide (which forms an electron dense precipitate at areas of cation binding), dehydrated and infiltrated with SpurrR epoxy resin. Individual nerve fibers were microdissected and counts made of the numbers of paranodal and nodal areas exhibiting the reaction product. The percentage of nodes stained, with respect to the total numbers of nodes and paranodes stained, was calculated. There was no significant difference in percent of nodes stained between the simultaneously fixed, non-stimulated, anesthetized (43.1%), the non-stimulated unanesthetized (45.3%), the animals stimulated at 10/sec (45.9%) and the animals stimulated at 30/sec (50.2%) and 100/sec(46.0%), and fixed post-stimulation. However, all values at the higher frequencies and fixed during stimulation were significantly different both from the control and from each other (30/sec-59.3%; 100/sec-70.5%; and 500/sec-76.4%). The location of cation binding appears to change in response to electrical stimulation and correlates with the increased frequency of the inward movement of sodium ions. PMID:7104729

  3. Cationic polyelectrolyte-stabilized nanoparticles via RAFT aqueous dispersion polymerization.

    PubMed

    Semsarilar, M; Ladmiral, V; Blanazs, A; Armes, S P

    2013-06-18

    We report the synthesis of cationic sterically stabilized diblock copolymer nanoparticles via polymerization-induced self-assembly (PISA) using a RAFT aqueous dispersion polymerization formulation. The cationic steric stabilizer is a macromolecular chain-transfer agent (macro-CTA) based on quaternized poly(2-(dimethylamino)ethyl methacrylate) (PQDMA), and the hydrophobic core-forming block is based on poly(2-hydroxypropyl methacrylate) (PHPMA). The effect of varying synthesis parameters such as the salt concentration, solids content, relative block composition, and cationic charge density has been studied. In the absence of salt, self-assembly is problematic because of the strong repulsion between the highly cationic PQDMA stabilizer chains. However, in the presence of salt this problem can be overcome by reducing the charge density within the coronal stabilizer layer by either (i) statistically copolymerizing QDMA monomer with a nonionic comonomer (e.g., glycerol monomethacrylate, GMA) or (ii) using a binary mixture of a PQDMA macro-CTA and a poly(glycerol monomethacrylate) (PGMA) macro-CTA. These cationic diblock copolymer nanoparticles were analyzed by (1)H NMR spectroscopy, dynamic light scattering (DLS), transmission electron microscopy (TEM), and aqueous electrophoresis. NMR studies suggest that the HPMA polymerization is complete within 2 h at 70 °C. Depending on the specific reaction conditions, either spherical, wormlike or vesicular nanoparticles can be prepared with tunable cationic surface charge. PMID:23205729

  4. Photochemical generation, isomerization, and oxygenation of stilbene cation radicals

    SciTech Connect

    Lewis, F.D.; Bedell, A.M.; Dykstra, R.E.; Elbert, J.E. ); Gould, I.R.; Farid, S. )

    1990-10-24

    The cation radicals of cis- and trans-stilbene and several of their ring-substituted derivatives have been generated in solution directly by means of pulsed-laser-induced electron transfer to singlet cyanoanthracenes or indirectly via electron transfer from biphenyl to the singlet cyanoanthracene followed by secondary electron transfer from the stilbenes to the biphenyl cation radical. Transient absorption spectra of the cis- and trans-stilbene cation radicals generated by secondary electron transfer are similar to those previously obtained in 77 K matrices. Quantum yields for radical ion-pair cage escape have been measured for direct electron transfer from the stilbenes to three neutral and one charged singlet acceptor. These values increase as the ion-pair energy increases due to decreased rate constants for radical ion-pair return electron transfer, in accord with the predictions of Marcus theory for highly exergonic electron transfer. Cage-escape efficiencies are larger for trans- vs cis-stilbene cation radicals, possibly due to the greater extent of charge delocalization in the planar trans vs nonpolar cis cation radicals. Cage-escape stilbene cation radicals can initiate a concentration-dependent one way cis- {yields} trans-stilbene isomerization reaction.

  5. 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.

  6. Cation-π interactions in lipocalins: structural and functional implications.

    PubMed

    Gasymov, Oktay K; Abduragimov, Adil R; Glasgow, Ben J

    2012-04-10

    The cation-π interaction impacts protein folding, structural stability, specificity, and molecular recognition. Cation-π interactions have been overlooked in the lipocalin family. To fill this gap, these interactions were analyzed in the 113 crystal and solution structures from the lipocalin family. The cation-π interactions link previously identified structurally conserved regions and reveal new motifs, which are beyond the reach of a sequence alignment algorithm. Functional and structural significance of the interactions were tested experimentally in human tear lipocalin (TL). TL, a prominent and promiscuous lipocalin, has a key role in lipid binding at the ocular surface. Ligand binding modulation through the loop AB at the "open" end of the barrel has been erroneously attributed solely to electrostatic interactions. Data revealed that the interloop cation-π interaction in the pair Phe28-Lys108 contributes significantly to stabilize the holo-conformation of the loop AB. Numerous energetically significant and conserved cation-π interactions were uncovered in TL and throughout the lipocalin family. Cation-π interactions, such as the highly conserved Trp17-Arg118 pair in TL, were educed in low temperature experiments of mutants with Trp to Tyr substitutions. PMID:22439821

  7. Cation-π Interactions in Lipocalins: Structural and Functional Implications

    PubMed Central

    Gasymov, Oktay K.; Abduragimov, Adil R.; Glasgow, Ben J.

    2013-01-01

    The cation-π interaction impacts protein folding, structural stability, specificity, and molecular recognition. Cation-π interactions have been overlooked in the lipocalin family. To fill this gap, these interactions were analyzed in the 113 crystal and solution structures from the lipocalin family. The cation-π interactions link previously identified structurally conserved regions and reveal new motifs, which are beyond the reach of a sequence alignment algorithm. Functional and structural significance of the interactions were tested experimentally in human tear lipocalin (TL). TL, a prominent and promiscuous lipocalin, has a key role in lipid binding at the ocular surface. Ligand binding modulation through the loop AB at the “open” end the barrel has been erroneously attributed solely to electrostatic interactions. Data revealed that the interloop cation-π interaction in the pair Phe28-Lys108 contributes significantly to stabilize the holo-conformation of the loop AB. Numerous energetically significant and conserved cation-π interactions were uncovered in TL and throughout the lipocalin family. Cation-π interactions, such as the highly conserved Trp17-Arg118 pair in TL, were educed in low temperature experiments of mutants with Trp to Tyr substitutions. PMID:22439821

  8. Mechanism for radical cation transport in duplex DNA oligonucleotides.

    PubMed

    Liu, Chu-Sheng; Hernandez, Rigoberto; Schuster, Gary B

    2004-03-10

    We investigated the photoinduced one-electron oxidation of a series of DNA oligomers having a covalently linked anthraquinone group (AQ) and containing [(A)(n)GG](m) or [(T)(n)GG](m) segments. These oligomers have m GG steps, where m = 4 or 6, separated by (A)(n) or (T)(n) segments, where n = 1-7 for the (A)(n) set and 1-5 for the (T)(n) set. Irradiation with UV light that is absorbed by the AQ causes injection of a radical cation into the DNA. The radical cation migrates through the DNA, causing chemical reaction, primarily at GG steps, that leads to strand cleavage after piperidine treatment. The uniform, systematic structure of the DNA oligonucleotides investigated permits the numerical solution of a kinetic scheme that models these reactions. This analysis yields two rate constants, k(hop), for hopping of the radical cation from one site to adjacent sites, and k(trap), for irreversible reaction of the radical cation with H(2)O or O(2). Analysis of these findings indicates that radical cation hopping in these duplex DNA oligomers is a process that occurs on a microsecond time scale. The value of k(hop) depends on the number of base pairs in the (A)(n) and (T)(n) segments in a systematic way. We interpret these results in terms of a thermally activated adiabatic mechanism for radical cation hopping that we identify as phonon-assisted polaron hopping. PMID:14995205

  9. Cation-binding Capacity of Membranes Isolated from Micrococcus lysodeikticus

    PubMed Central

    Cutinelli, C.; Galdiero, F.; Tufano, M. A.

    1969-01-01

    A study was made of H+, Na+, K+, Ca++, and Mg++ binding and ion-exchange properties of the plasma-mesosome membrane system isolated from Micrococcus lysodeikticus strain NCTC 2665. Titration curves were obtained on membranes prepared according to the method of M. R. J. Salton and further exposed to pH 4 for 4 hr (membranes-H). The dissociation coefficients and binding capacities were obtained by applying the mass law equation and the plot of G. Schatchard to the data. The membranes-H possess four kinds of dissociable groups with pK 4.96, 4.18, 3.60, and 3.09, respectively, and a total binding capacity of 0.65 meq/g (dry weight). Potentiometric titrations of cations in the presence and in the absence of membranes-H show that cations (Na+, K+, Ca++, and Mg++) are bound by the dissociated groups of the membrane. The fall in pH value for bivalent cations is greater than that for monovalent cations. Cations of the same valency produce equal diminutions on pH. Furthermore, ion-exchange tests carried out on membranes saturated with Mg++ or Na+ and suspended in a medium containing 45Ca show that the cations are reversibly bound. PMID:5344091

  10. Tunable states of interlayer cations in two-dimensional materials

    SciTech Connect

    Sato, K.; Numata, K.; Dai, W.; Hunger, M.

    2014-03-31

    The local state of cations inside the Ångstrom-scale interlayer spaces is one of the controlling factors for designing sophisticated two-dimensional (2D) materials consisting of 2D nanosheets. In the present work, the molecular mechanism on how the interlayer cation states are induced by the local structures of the 2D nanosheets is highlighted. For this purpose, the local states of Na cations in inorganic 2D materials, in which the compositional fluctuations of a few percent are introduced in the tetrahedral and octahedral units of the 2D nanosheets, were systematically studied by means of {sup 23}Na magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) and {sup 23}Na multiple-quantum MAS (MQMAS) NMR spectroscopy. In contrast with an uniform distribution of Na cations expected so far, various well-defined cation states sensitive to the local structures of the 2D nanosheets were identified. The tunability of the interlayer cation states along with the local structure of the 2D nanosheets, as the smallest structural unit of the 2D material, is discussed.

  11. Complexation Between Cationic Diblock Copolymers and Plasmid DNA

    NASA Astrophysics Data System (ADS)

    Jung, Seyoung; Reineke, Theresa; Lodge, Timothy

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

  12. Effect of cation exchange on surfactant-enhanced solubilization of trichloroethene

    NASA Astrophysics Data System (ADS)

    Field, J. A.; Sawyer, T. E.; Schroth, M. H.; Humphrey, M. D.; Istok, J. D.

    2000-11-01

    The objective of this study was to develop the single-well push-pull test as a diagnostic tool for assessing the potential for cation exchange to adversely affect the phase behavior of sodium dihexyl sulfosuccinate surfactant (Aerosol MA 80-I) and its solubilization of trichloroethene (TCE) in the subsurface. Laboratory push-pull tests were conducted on a model natural aquifer sediment collected from a TCE-contaminated field site and a test solution consisting of 36,800 mg/l (3.7 wt.%) sulfosuccinate, 100,000 mg/l (10 wt.%) isopropanol, and 3200 mg/l (0.32 wt.%) KBr. Laboratory experiments were designed to simulate conditions occurring during single-well, "push-pull" tests. In batch experiments conducted in the presence of excess TCE, the test solution gave a Winsor Type I system with an enhanced aqueous TCE solubility of 26,700 mg/l and a solution density of 1.000 g/cm 3. The sulfosuccinate surfactant was transported conservatively in sediment packs containing no TCE. However, increasing concentrations of Ca 2+ and Mg 2+ resulting from cation exchange caused the TCE solubilization potential of the injected surfactant to exceed values predicted from the solubilization isotherm. Sulfosuccinate surfactant transport was strongly retarded in sediment packs containing 5 vol.% residual TCE because cation exchange resulted in the formation of a Winsor Type II system, which resulted in the partitioning of the sulfosuccinate surfactant into the residual TCE phase. Conservative sulfosuccinate transport was observed in a separate sediment pack containing 5 vol.% residual TCE when a 130 meq/l Na + pre-flush was used to reduce quantities of Ca 2+ and Mg 2+ in the sediment pack prior to sulfosuccinate injection. The results of this study emphasize the importance of cation exchange on the performance of surfactant-enhanced TCE solubilization and demonstrate the utility of the push-pull test for predicting the potentially deleterious effects of cation exchange on surfactant phase

  13. Biogenic and synthetic polyamines bind cationic dendrimers.

    PubMed

    Mandeville, Jean-Sebastian; Bourassa, Phillipe; Thomas, Thekkumkattil John; Tajmir-Riahi, Heidar-Ali

    2012-01-01

    Biogenic polyamines are essential for cell growth and differentiation, while polyamine analogues exert antitumor activity in multiple experimental model systems, including breast and lung cancer. Dendrimers are widely used for drug delivery in vitro and in vivo. We report the bindings of biogenic polyamines, spermine (spm), and spermidine (spmd), and their synthetic analogues, 3,7,11,15-tetrazaheptadecane.4HCl (BE-333) and 3,7,11,15,19-pentazahenicosane.5HCl (BE-3333) to dendrimers of different compositions, mPEG-PAMAM (G3), mPEG-PAMAM (G4) and PAMAM (G4). FTIR and UV-visible spectroscopic methods as well as molecular modeling were used to analyze polyamine binding mode, the binding constant and the effects of polyamine complexation on dendrimer stability and conformation. Structural analysis showed that polyamines bound dendrimers through both hydrophobic and hydrophilic contacts with overall binding constants of K(spm-mPEG-G3) = 7.6 × 10(4) M(-1), K(spm-mPEG-PAMAM-G4) = 4.6 × 10(4) M(-1), K(spm-PAMAM-G4) = 6.6 × 10(4) M(-1), K(spmd-mPEG-G3) = 1.0 × 10(5) M(-1), K(spmd-mPEG-PAMAM-G4) = 5.5 × 10(4) M(-1), K(spmd-PAMAM-G4) = 9.2 × 10(4) M(-1), K(BE-333-mPEG-G3) = 4.2 × 10(4) M(-1), K(Be-333-mPEG-PAMAM-G4) = 3.2 × 10(4) M(-1), K(BE-333-PAMAM-G4) = 3.6 × 10(4) M(-1), K(BE-3333-mPEG-G3) = 2.2 × 10(4) M(-1), K(Be-3333-mPEG-PAMAM-G4) = 2.4 × 10(4) M(-1), K(BE-3333-PAMAM-G4) = 2.3 × 10(4) M(-1). Biogenic polyamines showed stronger affinity toward dendrimers than those of synthetic polyamines, while weaker interaction was observed as polyamine cationic charges increased. The free binding energies calculated from docking studies were: -3.2 (spermine), -3.5 (spermidine) and -3.03 (BE-3333) kcal/mol, with the following order of binding affinity: spermidine-PAMAM-G-4>spermine-PAMMAM-G4>BE-3333-PAMAM-G4 consistent with spectroscopic data. Our results suggest that dendrimers can act as carrier vehicles for delivering antitumor polyamine analogues to target tissues

  14. Ion-exchangeable, electronically conducting layered perovskite oxyfluorides.

    PubMed

    Kobayashi, Yoji; Tian, Mingliang; Eguchi, Miharu; Mallouk, Thomas E

    2009-07-22

    Cation-exchangeable d(0) layered perovskites are amenable to intercalation, exfoliation, and a variety of topochemical reactions, but they lack the interesting electronic and magnetic functionalities of mixed-valent perovskites. Conversely, electronically and magnetically interesting layered perovskites lack scope in terms of interlayer chemistry. To bridge this gap, the insulating, cation-exchangeable layered perovskites RbLaNb(2)O(7), KCa(2)Nb(3)O(10), and NaYTiO(4) were reacted with poly(tetrafluoroethylene) under inert atmosphere conditions to yield layer perovskites in which some of the oxygen is substituted by fluorine. In the fluorinated materials, the B-site cations are reduced to a mixed-valent state without introducing oxygen vacancies into the anion sublattice. The resulting electronically conducting solids can be exposed to air and water and even ion-exchanged in acid without oxidation of the B-site cations. Electronic transport measurements on the air-stable RbLaNb(2)O(6)F reveal room-temperature conductivity (2-7 x 10(2) ohms x cm) via a variable-range hopping mechanism, which is not substantially changed after aqueous proton exchange to H(1-x)Rb(x)LaNb(2)O(6)F (x approximately = 0.2). PMID:19548670

  15. Bimolecular Coupling Reactions through Oxidatively Generated Aromatic Cations: Scope and Stereocontrol

    PubMed Central

    Cui, Yubo; Villafane, Louis A.; Clausen, Dane J.

    2013-01-01

    Chromenes, isochromenes, and benzoxathioles react with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone to form stable aromatic cations that react with a range of nucleophiles. These oxidative fragment coupling reactions provide rapid access to structurally diverse heterocycles. Conducting the reactions in the presence of a chiral Brønsted acid results in the formation of an asymmetric ion pair that can provide enantiomerically enriched products in a rare example of a stereoselective process resulting from the generation of a chiral electrophile through oxidative carbon–hydrogen bond cleavage. PMID:23913987

  16. 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. PMID:23721117

  17. Ca2+ and Mn2+ Influx Through Receptor-Mediated Activation of Nonspecific Cation Channels in Mast Cells

    NASA Astrophysics Data System (ADS)

    Fasolato, Cristina; Hoth, Markus; Matthews, Gary; Penner, Reinhold

    1993-04-01

    Whole-cell patch-clamp recordings of membrane currents and Fura-2 measurements of free intracellular calcium concentration ([Ca2+]_i) were used to study calcium influx through receptor-activated cation channels in rat peritoneal mast cells. Cation channels were activated by the secretagogue compound 48/80, whereas a possible concomitant Ca2+ entry through pathways activated by depletion of calcium stores was blocked by dialyzing cells with heparin. Heparin effectively suppressed the transient Ca2+ release induced by 48/80 and abrogated inositol 1,4,5-trisphosphate-induced calcium influx without affecting activation of 50-pS cation channels. There was a clear correlation between changes in [Ca2+]_i and the activity of 50-pS channels. The changes in [Ca2+]_i increased with elevation of extracellular Ca2+. At the same time, inward currents through 50-pS channels were diminished as more Ca2+ permeated. This effect was due to a decrease in slope conductance and a reduction in the open probability of the cation channels. In physiological solutions, 3.6% of the total current was carried by Ca2+. The cation channels were not only permeable to Ca2+ but also to Mn2+, as evidenced by the quench of Fura-2 fluorescence. Mn2+ current through 50-pS channels could not be resolved at the single-channel level. Our results suggest that 50-pS cation channels partially contribute to sustained increases of [Ca2+]_i in mast cells following receptor activation.

  18. Mechanosensory calcium-selective cation channels in epidermal cells

    NASA Technical Reports Server (NTRS)

    Ding, J. P.; Pickard, B. G.

    1993-01-01

    This paper explores the properties and likely functions of an epidermal Ca(2+)-selective cation channel complex activated by tension. As many as eight or nine linked or linkable equivalent conductance units or co-channels can open together. Open time for co-channel quadruplets and quintuplets tends to be relatively long with millimolar Mg2+ (but not millimolar Ca2+) at the cytosolic face of excised plasma membrane. Sensitivity to tension is regulated by transmembrane voltage and temperature. Under some circumstances channel activity is sychronized in rhythmic pulses. Certain lanthanides and a cytoskeleton-disturbing herbicide that inhibit gravitropic reception act on the channel system at low concentrations. Specifically, ethyl-N-phenylcarbamate promotes tension-dependent activity at micromolar levels. With moderate suction, Gd3+ provided at about 0.5 micromole at the extracellular face of the membrane promotes for several seconds but may then become inhibitory. Provision at 1-2 micromoles promotes and subsequently inhibits more vigorously (often abruptly and totally), and at high levels inhibits immediately. La3+, a poor gravitropic inhibitor, acts similarly but much more gradually and only at much higher concentrations. These properties, particularly these susceptibilities to modulation, indicate that in vivo the mechanosensitive channel must be mechanosensory and mechanoregulatory. It could serve to transduce the shear forces generated in the integrated wall-membrane-cytoskeleton system during turgor changes and cell expansion as well as transducing the stresses induced by gravity, touch and flexure. In so far as such transduction is modulated by voltage and temperature, the channels would also be sensors for these modalities as long as the wall-membrane-cytoskeleton system experiences mechanical stress.

  19. 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

  20. Conducting Compositions of Matter

    NASA Technical Reports Server (NTRS)

    Viswanathan, Tito (Inventor)

    1999-01-01

    The invention provides conductive compositions of matter, as well as methods for the preparation of the conductive compositions of matter, solutions comprising the conductive compositions of matter, and methods of preparing fibers or fabrics having improved anti-static properties employing the conductive compositions of matter.

  1. Conducting compositions of matter

    NASA Technical Reports Server (NTRS)

    Viswanathan, Tito (Inventor)

    2000-01-01

    The invention provides conductive compositions of matter, as well as methods for the preparation of the conductive compositions of matter, solutions comprising the conductive compositions of matter, and methods of preparing fibers or fabrics having improved anti-static properties employing the conductive compositions of matter.

  2. Interaction of Organic Cations with Organic Anion Transporters*

    PubMed Central

    Ahn, Sun-Young; Eraly, Satish A.; Tsigelny, Igor; Nigam, Sanjay K.

    2009-01-01

    Studies of the organic anion transporters (Oats) have focused mainly on their interactions with organic anionic substrates. However, as suggested when Oat1 was originally identified as NKT (Lopez-Nieto, C. E., You, G., Bush, K. T., Barros, E. J., Beier, D. R., and Nigam, S. K. (1997) J. Biol. Chem. 272, 6471–6478), since the Oats share close homology with organic cation transporters (Octs), it is possible that Oats interact with cations as well. We now show that mouse Oat1 (mOat1) and mOat3 and, to a lesser degree, mOat6 bind a number of “prototypical” Oct substrates, including 1-methyl-4-phenylpyridinium. In addition to oocyte expression assays, we have tested binding of organic cations to Oat1 and Oat3 in ex vivo assays by analyzing interactions in kidney organ cultures deficient in Oat1 and Oat3. We also demonstrate that mOat3 transports organic cations such as 1-methyl-4-phenylpyridinium and cimetidine. A pharmacophore based on the binding affinities of the tested organic cations for Oat3 was generated. Using this pharmacophore, we screened a chemical library and were able to identify novel cationic compounds that bound to Oat1 and Oat3. These compounds bound Oat3 with an affinity higher than the highest affinity compounds in the original set of prototypical Oct substrates. Thus, whereas Oat1, Oat3, and Oat6 appear to function largely in organic anion transport, they also bind and transport some organic cations. These findings could be of clinical significance, since drugs and metabolites that under normal physiological conditions do not bind to the Oats may undergo changes in charge and become Oat substrates during pathologic conditions wherein significant variations in body fluid pH occur. PMID:19737926

  3. The interaction of humic substances with cationic polyelectrolytes.

    PubMed

    Kam, S K; Gregory, J

    2001-10-01

    The anionic charge carried by aquatic humic substances plays a major part in their interaction with metal ions and other cationic species. Removal of such substances by coagulation and flocculation can be, at least partly, determined by charge neutralisation. In this work, the charge densities of a commercial humic acid and an aquatic humic extract have been investigated by studying their interactions with a series of synthetic cationic polyelectrolytes. These covered a range of charge densities and molecular weights. The techniques used were colloid titration by spectrophotometry and streaming current detection, and flocculation determined by colour removal and by an optical monitoring method. For a given cationic polyelectrolyte, all four methods gave charge densities for humic substances which were in good agreement. However, systematic differences in the apparent humic charge density were found, depending on the charge density of the cationic polyelectrolyte used. With low charge density polyelectrolytes, the apparent anionic charge of the humic substances was found to be low. With higher polyelectrolyte charge densities, the apparent humic substance charge density increases and reaches a limiting value when the polyelectrolyte charge is greater than about 3 meq/g. This indicates a non-stoichiometric interaction between the anionic sites of the humic substances and the cationic charges of the low-charge polyelectrolytes. Optimum flocculation of humics occurred with less cationic charge in the case of low-charge polyelectrolytes than those with higher charge density. However, the degree of removal was considerably better in the latter case. In all cases, the molecular weight of the cationic polyelectrolytes (over a range from about 50,000 to 15 million) appeared to have no effect on the results. PMID:11561615

  4. Electrical conductivity of Cs2CuCl4 crystals

    NASA Astrophysics Data System (ADS)

    Sorokin, N. I.

    2016-05-01

    The electrical conductivity of Cs2CuCl4 single crystals, synthesized by crystallization from aqueous solutions in the CsCl-CuCl2-H2O system, has been investigated. The temperature dependence of the electrical conductivity of crystals in a temperature range of 338-584 K exhibits no anomalies. The electrical transfer activation enthalpy is Δ H σ = 0.72 ± 0.05 eV and the conductivity is σ = 3 × 10-4 S/cm at 584 K. The most likely carriers in Cs2CuCl4 are Cs+ cations, which transfer electric charge according to the vacancy mechanism.

  5. Sulfur-containing hetero-calix[4]pyrroles as mercury(II) cation-selective receptors: thermodynamic aspects.

    PubMed

    de Namor, Angela F Danil; Abbas, Ismail

    2007-05-31

    Two sulfur-containing hybrid calix[4]pyrrole derivatives (III and IV) have been synthesized and fully characterized. Several analytical techniques (1H NMR, conductance measurements, UV-vis spectrophotometry, titration potentiometry, and titration calorimetry) have been used to assess the interaction between these hybrid calixpyrrole receptors and metal cations in acetonitrile and dimethylsulfoxide. The partition constants of calix[4]pyrrole, I, II, and IV in the acetonitrile-hexane solvent system and the solubilities of the ligands in various solvents at 298.15 K were determined. 1H NMR measurements reveal the sites of interaction of calixpyrrole ligands with metal cations in CD3CN. Conductance and UV-vis spectrophotometric measurements were performed to establish the composition of mercury(II) calixpyrrole complexes in acetonitrile at 298.15 K. Titration calorimetry was used to quantitatively assess Hg(II)-calixpyrrole interactions. Thus the thermodynamics of complexation of calixpyrrole ligands with the mercury(II) cation in acetonitrile at 298.15 K are reported. Potentiometric titrations were also used to establish the stepwise stability constants for the complexation of calix[3]thieno[1]pyrrole with the Hg(II) cation in acetonitrile at 298.15 K. The results show that replacement of one or more pyrrole units by thiophene rings in calix[4]pyrrole has tuned significantly the discrimination ability of these ligands between anions and enables the produced hybrid calixpyrroles to bind selectively with Hg(II) in acetonitrile. No interaction was observed between these ligands and other metal cations in acetonitrile. PMID:17477564

  6. Enhanced Mixed Electronic-Ionic Conductors through Cation Ordering

    SciTech Connect

    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’B2O5+x, where A = rare earth ion, Y and B = Ba, Sr were studied. 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 PrBaCo2O5+x and NdBaCo2O5+x, PrBaCo2-xFexO6- δ (x = 0, 0.5, 1.0, 1.5 and 2) and LnBaCoFeO6- δ (Ln = La, Pr, Nd, Sm, Eu and Gd), Sr3YCo4O10.5, YBaMn2O5+x. A0.5A’0.5BO3 (where A=Y, Sc, La, Ce, Pr, Nd, Pm, Sm; A’= Sr

  7. Conductive paper from lignocellulose wood microfibers coated with a nanocomposite of carbon nanotubes and conductive polymers

    NASA Astrophysics Data System (ADS)

    Agarwal, Mangilal; Xing, Qi; Shim, Bong Sup; Kotov, Nicholas; Varahramyan, Kody; Lvov, Yuri

    2009-05-01

    Composite nanocoating of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS) and aqueous dispersion of carbon nanotubes (CNT-PSS) on lignocellulose wood microfibers has been developed to make conductive microfibers and paper sheets. To construct the multilayers on wood microfibers, cationic poly(ethyleneimine) (PEI) has been used in alternate deposition with anionic conductive PEDOT-PSS and solubilized CNT-PSS. Using a Keithley microprobe measurement system, current-voltage measurements have been carried out on single composite microfibers after deposition of each layer to optimize the electrical properties of the coated microfibers. The conductivity of the resultant wood microfibers was in the range of 10-2-2 S cm-1 depending on the architecture of the coated layer. Further, the conductivity of the coated wood microfibers increased up to 20 S cm-1 by sandwiching multilayers of conductive co-polymer PEDOT-PSS with CNT-PSS through a polycation (PEI) interlayer. Moreover, paper hand sheets were manufactured from these coated wood microfibers with conductivity ranging from 1 to 20 S cm-1. A paper composite structure consisting of conductive/dielectric/conductive layers that acts as a capacitor has also been fabricated and is reported.

  8. Phylogenetic relationships within cation transporter families of Arabidopsis.

    PubMed

    Mäser, P; Thomine, S; Schroeder, J I; Ward, J M; Hirschi, K; Sze, H; Talke, I N; Amtmann, A; Maathuis, F J; Sanders, D; Harper, J F; Tchieu, J; Gribskov, M; Persans, M W; Salt, D E; Kim, S A; Guerinot, M L

    2001-08-01

    Uptake and translocation of cationic nutrients play essential roles in physiological processes including plant growth, nutrition, signal transduction, and development. Approximately 5% of the Arabidopsis genome appears to encode membrane transport proteins. These proteins are classified in 46 unique families containing approximately 880 members. In addition, several hundred putative transporters have not yet been assigned to families. In this paper, we have analyzed the phylogenetic relationships of over 150 cation transport proteins. This analysis has focused on cation transporter gene families for which initial characterizations have been achieved for individual members, including potassium transporters and channels, sodium transporters, calcium antiporters, cyclic nucleotide-gated channels, cation diffusion facilitator proteins, natural resistance-associated macrophage proteins (NRAMP), and Zn-regulated transporter Fe-regulated transporter-like proteins. Phylogenetic trees of each family define the evolutionary relationships of the members to each other. These families contain numerous members, indicating diverse functions in vivo. Closely related isoforms and separate subfamilies exist within many of these gene families, indicating possible redundancies and specialized functions. To facilitate their further study, the PlantsT database (http://plantst.sdsc.edu) has been created that includes alignments of the analyzed cation transporters and their chromosomal locations. PMID:11500563

  9. 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.

  10. Electrospray Ionization Tandem Mass Spectrometry of Ammonium Cationized Polyethers

    NASA Astrophysics Data System (ADS)

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

    2011-05-01

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

  11. Cationic polymers and their self-assembly for antibacterial applications.

    PubMed

    Deka, Smriti Rekha; Sharma, Ashwani Kumar; Kumar, Pradee

    2015-01-01

    The present article focuses on the amphiphilic cationic polymers as antibacterial agents. These polymers undergo self-assembly in aqueous conditions and impart biological activity by efficiently interacting with the bacterial cell wall, hence, used in preparing chemical disinfectants and biocides. Both cationic charge as well as hydrophobic segments facilitate interactions with the bacterial cell surface and initiate its disruption. The perturbation in transmembrane potential causes leakage of cytosolic contents followed by cell death. Out of two categories of macromolecules, peptide oligomers and cationic polymers, which have extensively been used as antibacterials, we have elaborated on the current advances made in the area of cationic polymer-based (naturally occurring and commonly employed synthetic polymers and their modified analogs) antibacterial agents. The development of polymer-based antibacterials has helped in addressing challenges posed by the drug-resistant bacterial infections. These polymers provide a new platform to combat such infections in the most efficient manner. This review presents concise discussion on the amphiphilic cationic polymers and their modified analogs having low hemolytic activity and excellent antibacterial activity against array of fungi, bacteria and other microorganisms. PMID:25858132

  12. [Cation exchanges during the process of Cd(2+) absorption by Alfalfa in aqueous solutions].

    PubMed

    Li, Yue-Peng; Yin, Hua; Ye, Jin-Shao; Peng, Hua; Qin, Hua-Ming; Long, Yan; He, Bao-Yan; Zhang, Na; Tong, Yao; Peng, Su-Fen

    2011-11-01

    A hydroponic experiment was conducted to investigate the cation exchanges during the process of Cd2+ absorption by Alfalfa in aqueous solution. The absorption efficiency of Alfalfa plants with 0-10 mg x L(-1) Cd2+ treatments, changes of Na+, K+, Mg2+, Ca2+ and NH4(+) concentration, and the variation of pH values at different absorption time (0, 1, 2, 4, 8, 12, 24 and 72 h) were studied separately. The multiple linear regressions between Cd2+ absorption and cation variation were analyzed. The results indicated that when Cd2+ concentrations were 0.1, 1, 5, 10 mg x L(-1), the absorption efficiencies of Cd2+ by Alfalfa after 72 h were 85.86%, 52.14%, 15.97% and 7.81%. Cation exchange was involved in the removal of Cd2+ by Alfalfa in aqueous solution. Except for NH4(+), the concentrations of cationic metals Na+, K+, Mg2+ and Ca2+ in aqueous solution increased over time, which increased 11.30% - 61.72%, 21.44% - 98.73%, 24.09% - 8.90% and 37.04% - 191.96%, respectively. Kinetic studies illuminated that the release of Na+, K+, Mg2+ and Ca2+ by Alfalfa in Cd2+ solution with initial concentrations of 0, 0. 1, 1, 5, 10 mg x L(-1) best fitted pseudo-second-order equation,while the NH4(+) release fitted this model when Cd2+ concentrations were 1, 5, 10 mg x L(-1). The gradual decrease of pH during adsorption of Cd2+ by Alfalfa was observed. As the competition ion of Cd2+, H+ might affect the capacity of Alfalfa root system to absorb Cd2+. The ternary linear equation results demonstrated that the content of Cd2+ absorption by Alfalfa strongly related with the release of Ca2+, Mg2+, Na+. And this exchange mainly occurred among Cd2+ and divalent cations. PMID:22295633

  13. Influence of Cation Size on the Ionicity, Fluidity, and Physiochemical Properties of 1,2,4-Triazolium Based Ionic Liquids.

    PubMed

    Singh, Dharmendra; Gardas, Ramesh L

    2016-06-01

    Interpreting the physiochemical properties and structure-property correlations of ionic liquids (ILs) is a key to the enlargement of their optimized structures for specific applications. In this work, a series of ILs based on 1-alkyl-1,2,4-triazolium cation with trifluoromethanesulfonate anion were synthesized and the effect of cation and temperature on physiochemical properties such as density, viscosity, speed of sound, conductivity, and rheology was studied. Temperature dependence densities were correlated with the densities estimated by the Gardas and Coutinho model, whereas viscosity and molar conductivity have been found to satisfy the Vogel-Tammann-Fulcher (VTF) equation over the studied temperature range 293.15-343.15 K. Further, to explore the wide range of applications, ionicity has been tested by correlating the fluidity with molar conductivity and it was found that synthesized ILs can be referred to as "good ILs". Furthermore, the fluidity behavior describing the interactions between the cation and anion of ILs was investigated through their rheological properties, and the Newtonian behavior of ILs has been examined by varying the effect of shear rate on viscosity. Finally, the impact of structure variants in terms of the N-1 functionalized 1,2,4-triazole ring has been analyzed over the studied properties. PMID:27158831

  14. Prepared polymethacrylate-based monoliths for the separation of cations by non-suppressed capillary ion chromatography.

    PubMed

    Li, Jing; Zhu, Yan

    2014-01-01

    This paper describes a novel analytical system for non-suppressed capillary ion chromatography. Methacrylate monolithic columns were prepared from silanized fused-silica capillaries of 320 µm i.d. by in situ polymerization of glycidyl methacrylate and ethylene dimethacrylate in the presence of 1,4-butanediol, 1-propanol and water as the porogen solvents. The introduction of cation-exchange sites was achieved by sulfonating the matrix with sodium sulfite to produce total cation-exchange capacities in the range of 45-105 μequiv/mL for a 25 cm column. The conditions (concentrations of sodium sulfite solution, reacting time and modified flow rate) of sulfonation were optimized. The hydrodynamic and chromatographic performances were estimated. Coupled with a conductivity detector, a capillary ion chromatography system was set up with the prepared column. Finally, the resultant column was used for the separations of five common univalent cations (Li(+), Na(+), NH4(+), K(+) and Cs(+)) using methanesulfonic acid as the eluent and four divalent cations (Mg(2+), Ca(2+), Sr(2+) and Ba(2+)) by non-suppressed capillary ion chromatography; the chromatographic parameters were further researched. PMID:23677716

  15. Nerve conduction velocity

    MedlinePlus

    Nerve conduction velocity (NCV) is a test to see how fast electrical signals move through a nerve. ... normal body temperature. Being too cold slows nerve conduction. Tell your doctor if you have a cardiac ...

  16. Nerve conduction velocity

    MedlinePlus

    ... page: //medlineplus.gov/ency/article/003927.htm Nerve conduction velocity To use the sharing features on this page, please enable JavaScript. Nerve conduction velocity (NCV) is a test to see how ...

  17. The Conductivity of Solutions.

    ERIC Educational Resources Information Center

    Rayner-Canham, Geoff

    1993-01-01

    Presents historical background and modern explanations for the popular demonstration of showing conductivity of solutions through the insertion of a light-bulb conductivity tester into deionized water and water with salt in it. (PR)

  18. Computational Studies of Gramicidin Permeation: An Entryway Sulfonate Enhances Cation Occupancy at Entry Sites

    PubMed Central

    Mustafa, Morad; Henderson, Douglas J.; Busath, David D.

    2009-01-01

    The impact on the cation-transport free-energy profile of replacing the C-terminal ethanolamine in the gramicidin A channel with a taurine residue is studied using molecular dynamics simulations of gramicidin A (1JNO) embedded in a lipid bilayer (DMPC) with 1 mol/kg NaCl saline solution. The potential of mean force for ion transport is obtained by umbrella sampling. The presence of a negatively charged sulfonate group at the entrance of the gramicidin channel affects the depth and the location of the binding sites, producing a strong attraction for the cations in the bulk. The potential of mean force by the sulfonate acting directly through electrostatics and van der Waals interactions on the test ion is highly modulated by indirect effects (i.e., sulfonate effects on other components of the system that, in turn, affect the ion free-energy profile in the channel). Because the “entry” sites are located symmetrically at both entry and exit of the channel, the deeper free-energy wells should inhibit exit. Given that the channel has increased conductance experimentally, the simulation results suggest that the channel conductance is normally entry limited. PMID:19361485

  19. Characterization of an inward rectifying cationic channel in onion guard cell vacuoles

    SciTech Connect

    Amodeo, G.; Zeiger, E.; Escobar, A. )

    1993-05-01

    Ion channels modulate the large ion fluxes across the guard cell plasma membrane and tonoplast that are required for stomatal movement. In contrast to the well known ion channels at the plasma membrane, those at the guard cell tonoplast have not been described. We used patch clamping with guard cell protoplasts (GCP) from Allium cepa cotyledons to study channels from isolated tonoplast patches. The GCPs, obtained after a brief digestion time, released their vacuoles when exposed to an osmotic shock in the presence of EGTA. In inside-out patches bathed in symmetrical solutions (200 mM KCl as predominant ion) a 207[plus minus]1.6 pS channel was the most frequently observed. The channel was activated at negative potential and showed a very large rectification in the open probability in the absence of divalent cations in the vacuolar side. Replacement of monovalent ions in the bath solution gave a sequence of selectivity: Na[sup +]>K[sup +]>Rb[sup +]>Cs[sup +]. Both conduction and gating were investigated at the single channel level. Pulse protocols were achieved for the kinetic analysis of the activation and deactivation of the ionic channel. Records at different potentials were averaged to generate the ensemble profile of the macroscopic conductance. The analysis showed that this channel has at least one closed state and two open states. We suggest that this predominant inward rectifying cationic channel has an important role in the modulation of fluxes between the vacuole and cytosol of guard cells.

  20. All-inorganic Germanium nanocrystal films by cationic ligand exchange

    DOE PAGESBeta

    Wheeler, Lance M.; Nichols, Asa W.; Chernomordik, Boris D.; Anderson, Nicholas C.; Beard, Matthew C.; Neale, Nathan R.

    2016-01-21

    In this study, we introduce a new paradigm for group IV nanocrystal surface chemistry based on room temperature surface activation that enables ionic ligand exchange. Germanium nanocrystals synthesized in a gas-phase plasma reactor are functionalized with labile, cationic alkylammonium ligands rather than with traditional covalently bound groups. We employ Fourier transform infrared and 1H nuclear magnetic resonance spectroscopies to demonstrate the alkylammonium ligands are freely exchanged on the germanium nanocrystal surface with a variety of cationic ligands, including short inorganic ligands such as ammonium and alkali metal cations. This ionic ligand exchange chemistry is used to demonstrate enhanced transport inmore » germanium nanocrystal films following ligand exchange as well as the first photovoltaic device based on an all-inorganic germanium nanocrystal absorber layer cast from solution. This new ligand chemistry should accelerate progress in utilizing germanium and other group IV nanocrystals for optoelectronic applications.« less

  1. Cation-halide transport through peptide pores containing aminopicolinic acid.

    PubMed

    Basak, Debajyoti; Sridhar, Sucheta; Bera, Amal K; Madhavan, Nandita

    2016-05-18

    Synthetic pores that selectively transport ions of biological significance through membranes could be potentially used in medical diagnostics or therapeutics. Herein, we report cation-selective octapeptide pores derived from alanine and aminopicolinic acid. The ion transport mechanism through the pores has been established to be a cation-chloride symport. The cation-chloride co-transport is biologically essential for the efficient functioning of the central nervous system and has been implicated in diseases such as epilepsy. The pores formed in synthetic lipid bilayers do not exhibit any closing events. The ease of synthesis as well as infinite lifetimes of these pores provides scope for modifying their transport behaviour to develop sensors. PMID:27137995

  2. Low-Temperature Cationic Rearrangement in a Bulk Metal Oxide.

    PubMed

    Li, Man-Rong; Retuerto, Maria; Stephens, Peter W; Croft, Mark; Sheptyakov, Denis; Pomjakushin, Vladimir; Deng, Zheng; Akamatsu, Hirofumi; Gopalan, Venkatraman; Sánchez-Benítez, Javier; Saouma, Felix O; Jang, Joon I; Walker, David; Greenblatt, Martha

    2016-08-16

    Cationic rearrangement is a compelling strategy for producing desirable physical properties by atomic-scale manipulation. However, activating ionic diffusion typically requires high temperature, and in some cases also high pressure in bulk oxide materials. Herein, we present the cationic rearrangement in bulk Mn2 FeMoO6 at unparalleled low temperatures of 150-300 (o) C. The irreversible ionic motion at ambient pressure, as evidenced by real-time powder synchrotron X-ray and neutron diffraction, and second harmonic generation, leads to a transition from a Ni3 TeO6 -type to an ordered-ilmenite structure, and dramatic changes of the electrical and magnetic properties. This work demonstrates a remarkable cationic rearrangement, with corresponding large changes in the physical properties in a bulk oxide at unprecedented low temperatures. PMID:27203790

  3. Nanoscale encapsulation: the structure of cations in hydrophobic microporous aluminosilicates

    SciTech Connect

    Wasserman, S.R.; Yuchs, S.E.; Giaquinta, D.; Soderholm, L.; Song, Kang

    1996-10-01

    Hydrophobic microporous aluminosilicates, created by organic surface modification of inherently hydrophilic materials such as zeolites and clays, are currently being investigated as storage media for hazardous cations. Use of organic monolayers to modify the surface of an aluminosilicate after introducing an ion into the zeolite/clay reduces the interaction of water with the material. Resulting systems are about 20 times more resistant to leaching of stored ion. XAS spectra from the encapsulated ion demonstrate that byproducts from the organic modifier can complex with the stored cation. This complexation can result in a decreased affinity of the cation for the aluminosilicate matrix. Changing the organic modifier eliminates this problem. XAS spectra also indicate that the reactivity and speciation of the encapsulated ion may change upon application of the hydrophobic layer.

  4. Solubility and transport of cationic and anionic patterned nanoparticles

    NASA Astrophysics Data System (ADS)

    Su, Jiaye; Guo, Hongxia; Olvera de La Cruz, Monica

    2012-02-01

    Diffusion and transport of nanoparticles (NPs) though nanochannels is important for desalination, drug delivery, and biomedicine. Their surface composition dictate their efficiency separating them by reverse osmosis, delivering into into cells, as well as their toxicity. We analyze bulk diffusion and transport through nanochannels of NPs with different hydrophobic-hydrophilic patterns achieved by coating a fraction of the NP sites with positive or negative charges via explicit solvent molecular dynamics simulations. The cationic NPs are more affected by the patterns, less water soluble, and have higher diffusion constants and fluxes than their anionic NPs counterparts. The NP-water interaction dependence on surface pattern and field strength explains these observations. For equivalent patterns, anionic NPs solubilize more than cationic NPs since the Coulomb interaction of free anionic NPs, which are much stronger than hydrophobic NP-water interactions, are about twice that of cationic NPs.

  5. All-Inorganic Germanium Nanocrystal Films by Cationic Ligand Exchange.

    PubMed

    Wheeler, Lance M; Nichols, Asa W; Chernomordik, Boris D; Anderson, Nicholas C; Beard, Matthew C; Neale, Nathan R

    2016-03-01

    We introduce a new paradigm for group IV nanocrystal surface chemistry based on room temperature surface activation that enables ionic ligand exchange. Germanium nanocrystals synthesized in a gas-phase plasma reactor are functionalized with labile, cationic alkylammonium ligands rather than with traditional covalently bound groups. We employ Fourier transform infrared and (1)H nuclear magnetic resonance spectroscopies to demonstrate the alkylammonium ligands are freely exchanged on the germanium nanocrystal surface with a variety of cationic ligands, including short inorganic ligands such as ammonium and alkali metal cations. This ionic ligand exchange chemistry is used to demonstrate enhanced transport in germanium nanocrystal films following ligand exchange as well as the first photovoltaic device based on an all-inorganic germanium nanocrystal absorber layer cast from solution. This new ligand chemistry should accelerate progress in utilizing germanium and other group IV nanocrystals for optoelectronic applications. PMID:26796765

  6. Surface Conductive Glass.

    ERIC Educational Resources Information Center

    Tanaka, John; Suib, Steven L.

    1984-01-01

    Discusses the properties of surface-conducting glass and the chemical nature of surface-conducting stannic (tin) oxide. Also provides the procedures necessary for the preparation of surface-conducting stannic oxide films on glass substrates. The experiment is suitable for the advanced inorganic chemistry laboratory. (JN)

  7. 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.

  8. Physicochemical and transfection properties of cationic Hydroxyethylcellulose/DNA nanoparticles.

    PubMed

    Fayazpour, Farzaneh; Lucas, Bart; Alvarez-Lorenzo, Carmen; Sanders, Niek N; Demeester, Jo; De Smedt, Stefaan C

    2006-10-01

    In this study the physicochemical and transfection properties of cationic hydroxyethylcellulose/plasmid DNA (pDNA) nanoparticles were investigated and compared with the properties of DNA nanoparticles based on polyethylene imine (PEI), which is widely investigated as a gene carrier. The two types of cationic hydroxyethylcelluloses studied, polyquaternium-4 (PQ-4) and polyquaternium-10 (PQ-10), are already commonly used in cosmetic and topical drug delivery devices. Both PQ-4 and PQ-10 spontaneously interact with pDNA with the formation of nanoparticles approximately 200 nm in size. Gel electrophoresis and fluorescence dequenching experiments indicated that the interactions between pDNA and the cationic celluloses were stronger than those between pDNA and PEI. The cationic cellulose/pDNA nanoparticles transfected cells to a much lesser extent than the PEI-based pDNA nanoparticles. The low transfection property of the PQ-4/pDNA nanoparticles was attributed to their neutrally charged surface, which does not allow an optimal binding of PQ-4/pDNA nanoparticles to cellular membranes. Although the PQ-10/pDNA nanoparticles were positively charged and thus expected to be taken up by cells, they were also much less efficient in transfecting cells than were PEI/pDNA nanoparticles. Agents known to enhance the endosomal escape were not able to improve the transfection properties of PQ-10/pDNA nanoparticles, indicating that a poor endosomal escape is, most likely, not the major reason for the low transfection activity of PQ-10/pDNA nanoparticles. We hypothesized that the strong binding of pDNA to PQ-10 prohibits the release of pDNA from PQ-10 once the PQ-10/pDNA nanoparticles arrive in the cytosol of the cells. Tailoring the nature and extent of the cationic side chains on this type of cationic hydroxyethylcellulose may be promising to further enhance their DNA delivery properties. PMID:17025362

  9. Modeling cation exchange using EQ3/6

    SciTech Connect

    Viani, B.; Bruton, C.; Bourcier, B.

    1992-08-01

    Geochemical modeling codes must be able to predict solid-solution and ion-exchange behavior of zeolites and smectites in order to design and assess strategies for containing and cleaning up toxic and/or radioactive wastes. Cation-exchange and solid-solution models have been implemented in the EQ3/6 geochemical modeling package and used to predict the composition of clinoptilolite under a variety of conditions. Published free energies of cation exchange on clinoptilolite at 25{degrees}C were combined with the calorimetric data for clinoptilolite to derive free energies of formation of the component end members of a solid solution in which mixing is allowed only on the exchange site. The solid-solution model and component end-member data were incorporated into EQ3/6 and its data base. An option to treat cation exchange independently of the solid-solution model was also developed and implemented in EQ3/6. This option allows the user to model mixed-phase exchangers, multisite exchangers, and systems in which the exchanger is not in overall equilibrium with the solution. Two {open_quotes}ideal{close_quotes} cation-exchange conventions [Vanselow (mole fraction) and Gapon (equivalent fraction)] are currently implemented in the code. A description of the cation-exchange models and their implementation into EQ3/6 is presented, and the relationship between the exchange formalisms and the solid-solution models is discussed. The advantages and limitations of the models and currently available thermodynamic data are addressed by comparing cation-exchange compositions of clinoptilolites with (1) published binary exchange data; (2) compositions of coexisting clinoptilolites and formation waters at Yucca Mountain; and (3) experimental sorption isotherms of Cs and Sr on zeolitized tuff.

  10. A Structural Electrical Conductivity Model for Oxide Melts

    NASA Astrophysics Data System (ADS)

    Thibodeau, Eric; Jung, In-Ho

    2016-02-01

    A structural electrical conductivity model for oxide melts was developed based on the Nernst-Einstein relationship of ionic conductivity. In the description of ionic conductivity, the effective diffusivities of cations in oxide slags were described as a function of the polymerization of the melt. The polymerization of oxide melts was calculated from the Modified Quasichemical Model, taking into account the short-range ordering in slags. The parameters of this conductivity model were fixed to reproduce the electrical conductivity data in unary and binary melts, and the model can well predict the conductivity data in ternary and higher order system without any additional model parameters. The model is successfully applied to the CaO-MgO-MnO-PbO-Al2O3-SiO2 system.

  11. Conduction properties of the cloned Shaker K+ channel.

    PubMed Central

    Heginbotham, L; MacKinnon, R

    1993-01-01

    The conduction properties of the cloned Shaker K+ channel were studied using electrophysiological techniques. Single channel conductance increases in a sublinear manner with symmetric increases in K+ activity, reaching saturation by 0.6 M K+. The Shaker K+ channel is highly selective among monovalent cations; under bi-ionic conditions, its selectivity sequence is K+ > Rb+ > NH+4 > Cs+ > Na+, whereas, by relative conductance in symmetric solutions, it is K+ > NH+4 > Rb+ > Cs+. In Cs+ solutions, single channel currents were too small to be measured directly, so nonstationary fluctuation analysis was used to determine the unitary Cs+ conductance. The single channel conductance displays an anomalous molefraction effect in symmetric mixtures of K+ and NH+4, suggesting that the conducting pore is occupied by multiple ions simultaneously. PMID:8298038

  12. Electrically conductive composite material

    DOEpatents

    Clough, Roger L.; Sylwester, Alan P.

    1989-01-01

    An electrically conductive composite material is disclosed which comprises a conductive open-celled, low density, microcellular carbon foam filled with a non-conductive polymer or resin. The composite material is prepared in a two-step process consisting of first preparing the microcellular carbon foam from a carbonizable polymer or copolymer using a phase separation process, then filling the carbon foam with the desired non-conductive polymer or resin. The electrically conductive composites of the present invention has a uniform and consistant pattern of filler distribution, and as a result is superior over prior art materials when used in battery components, electrodes, and the like.

  13. Electrically conductive composite material

    DOEpatents

    Clough, R.L.; Sylwester, A.P.

    1988-06-20

    An electrically conductive composite material is disclosed which comprises a conductive open-celled, low density, microcellular carbon foam filled with a non-conductive polymer or resin. The composite material is prepared in a two-step process consisting of first preparing the microcellular carbon foam from a carbonizable polymer or copolymer using a phase separation process, then filling the carbon foam with the desired non-conductive polymer or resin. The electrically conductive composites of the present invention has a uniform and consistent pattern of filler distribution, and as a result is superior over prior art materials when used in battery components, electrodes, and the like. 2 figs.

  14. Cationically polymerizable monomers derived from renewable sources. Annual performance report

    SciTech Connect

    Crivello, J.V.

    1992-10-01

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

  15. 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

  16. Crystalline, Lewis base-free, cationic phosphoranimines (iminophosphonium salts).

    PubMed

    Dielmann, Fabian; Moore, Curtis E; Rheingold, Arnold L; Bertrand, Guy

    2013-09-25

    Cationic phosphoranimines have been postulated as intermediates in phosphazene polymerization chemistry. However, the high electrophilicity of the phosphorus center has so far prevented their characterization. Here, we report the synthesis of two Lewis base-free iminophosphonium salts, obtained by reaction of a stable phosphinonitrene with methyl trifluoromethanesulfonate and trifluoromethanesulfonic acid. These cationic species were characterized by NMR spectroscopy and single-crystal X-ray diffraction analysis. Using 4-(dimethylamino)pyridine, a corresponding Lewis-base adduct has also been isolated. PMID:24007472

  17. M2 pore mutations convert the glycine receptor channel from being anion- to cation-selective.

    PubMed Central

    Keramidas, A; Moorhouse, A J; French, C R; Schofield, P R; Barry, P H

    2000-01-01

    Three mutations in the M2 transmembrane domains of the chloride-conducting alpha1 homomeric glycine receptor (P250Delta, A251E, and T265V), which normally mediate fast inhibitory neurotransmission, produced a cation-selective channel with P(Cl)/P(Na), = 0.27 (wild-type P(Cl)/P(Na) = 25), a permeability sequence P(Cs) > P(K) > P(Na) > P(Li), an impermeability to Ca(2+), and a reduced glycine sensitivity. Outside-out patch measurements indicated reversed and accentuated rectification with extremely low mean single channel conductances of 3 pS (inward current) and 11 pS (outward current). The three inverse mutations, to those analyzed in this study, have previously been shown to make the alpha7 acetylcholine receptor channel anion-selective, indicating a common location for determinants of charge selectivity of inhibitory and excitatory ligand-gated ion channels. PMID:10866951

  18. Improved Mechanical Properties and Sustained Release Behavior of Cationic Cellulose Nanocrystals Reinforeced Cationic Cellulose Injectable Hydrogels.

    PubMed

    You, Jun; Cao, Jinfeng; Zhao, Yanteng; Zhang, Lina; Zhou, Jinping; Chen, Yun

    2016-09-12

    Polysaccharide-based injectable hydrogels have several advantages in the context of biomedical use. However, the main obstruction associated with the utilization of these hydrogels in clinical application is their poor mechanical properties. Herein, we describe in situ gelling of nanocomposite hydrogels based on quaternized cellulose (QC) and rigid rod-like cationic cellulose nanocrystals (CCNCs), which can overcome this challenge. In all cases, gelation immediately occurred with an increase of temperature, and the CCNCs were evenly distributed throughout the hydrogels. The nanocomposite hydrogels exhibited increasing orders-of-magnitude in the mechanical strength, high extension in degradation and the sustained release time, because of the strong interaction between CCNCs and QC chains mediated by the cross-linking agent (β-glycerophosphate, β-GP). The results of the in vitro toxicity and in vivo biocompatibility tests revealed that the hydrogels did not show obvious cytotoxicity and inflammatory reaction to cells and tissue. Moreover, DOX-encapsulated hydrogels were injected beside the tumors of mice bearing liver cancer xenografts to assess the potential utility as localized and sustained drug delivery depot systems for anticancer therapy. The results suggested that the QC/CCNC/β-GP nanocomposite hydrogels had great potential for application in subcutaneous and sustained delivery of anticancer drug to increase therapeutic efficacy and improve patient compliance. PMID:27519472

  19. Ruminal and Abomasal Starch Hydrolysate Infusions Selectively Decrease the Expression of Cationic Amino Acid Transporter mRNA by Small Intestinal Epithelia of Forage-fed Beef Steers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Although cationic amino acids (CAA) are consid-ered essential to maximize optimal growth of cattle, transporters responsible for CAA absorption by bovine small intestinal epithelia have not been described. This study was conducted to test 2 hypotheses: 1) the duo¬denal, jejunal, and ileal epithelia ...

  20. Highly Stable, Anion Conductive, Comb-Shaped Copolymers for Alkaline Fuel Cells

    SciTech Connect

    Li, NW; Leng, YJ; Hickner, MA; Wang, CY

    2013-07-10

    To produce an anion-conductive and durable polymer electrolyte for alkaline fuel cell applications, a series of quaternized poly(2,6-dimethyl phenylene oxide)s containing long alkyl side chains pendant to the nitrogen-centered cation were synthesized using a Menshutkin reaction to form comb-shaped structures. The pendant alkyl chains were responsible for the development of highly conductive ionic domains, as confirmed by small-angle X-ray scattering (SAXS). The comb-shaped polymers having one alkyl side chain showed higher hydroxide conductivities than those with benzyltrimethyl ammonium moieties or structures with more than one alkyl side chain per cationic site. The highest conductivity was observed for comb-shaped polymers with benzyldimethylhexadecyl ammonium cations. The chemical stabilities of the comb-shaped membranes were evaluated under severe, accelerated-aging conditions, and degradation was observed by measuring IEC and ion conductivity changes during aging. The comb-shaped membranes retained their high ion conductivity in 1 M NaOH at 80 degrees C for 2000 h. These cationic polymers were employed as ionomers in catalyst layers for alkaline fuel cells. The results indicated that the C-16 alkyl side chain ionomer had a slightly better initial performance, despite its low IEC value, but very poor durability in the fuel cell. In contrast, 90% of the initial performance was retained for the alkaline fuel cell with electrodes containing the C-6 side chain after 60 h of fuel cell operation.

  1. Simultaneous micro-electromembrane extractions of anions and cations using multiple free liquid membranes and acceptor solutions.

    PubMed

    Kubáň, Pavel; Boček, Petr

    2016-02-18

    Micro-electromembrane extractions (μ-EMEs) across free liquid membranes (FLMs) were applied to simultaneous extractions of anions and cations. A transparent narrow-bore polymeric tubing was filled with adjacent plugs of μL volumes of aqueous and organic solutions, which formed a stable five-phase μ-EME system. For the simultaneous μ-EMEs of anions and cations, aqueous donor solution was the central phase, which was sandwiched between two organic FLMs and two aqueous acceptor solutions. On application of electric potential, anions and cations in the donor solution migrated across the two FLMs and into the two peripheral acceptor solutions in the direction of anode and cathode, respectively. Visual monitoring of anionic (tartrazine) and cationic (phenosafranine) dye confirmed their simultaneous μ-EMEs and their rapid (in less than 5 min) transfers into anolyte and catholyte, respectively. The concept of simultaneous μ-EMEs was further examined with selected model analytes; KClO4 was used for μ-EMEs of inorganic anions and cations and ibuprofen and procaine for μ-EMEs of acidic and basic drugs. Quantitative analyses of the resulting acceptor solutions were carried out by capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-C(4)D). Good extraction recoveries (91-94%) and repeatability of peak areas (≤6.3%) were achieved for 5 min μ-EMEs of K(+) and ClO4(-). Extraction recoveries and repeatability of peak areas for 5 min μ-EMEs of ibuprofen and procaine were also satisfactory and ranged from 35 to 63% and 7.6 to 11.3%, respectively. Suitability of the presented micro-extraction procedure was further demonstrated on simultaneous μ-EMEs with subsequent CE-C(4)D of ibuprofen and procaine from undiluted human urine samples. PMID:26826693

  2. High conductance surge cable

    DOEpatents

    Murray, Matthew M.; Wilfong, Dennis H.; Lomax, Ralph E.

    1998-01-01

    An electrical cable for connecting transient voltage surge suppressers to ectrical power panels. A strip of electrically conductive foil defines a longitudinal axis, with a length of an electrical conductor electrically attached to the metallic foil along the longitudinal axis. The strip of electrically conductive foil and the length of an electrical conductor are covered by an insulating material. For impedance matching purposes, triangular sections can be removed from the ends of the electrically conductive foil at the time of installation.

  3. High conductance surge cable

    DOEpatents

    Murray, M.M.; Wilfong, D.H.; Lomax, R.E.

    1998-12-08

    An electrical cable for connecting transient voltage surge suppressors to electrical power panels. A strip of electrically conductive foil defines a longitudinal axis, with a length of an electrical conductor electrically attached to the metallic foil along the longitudinal axis. The strip of electrically conductive foil and the length of an electrical conductor are covered by an insulating material. For impedance matching purposes, triangular sections can be removed from the ends of the electrically conductive foil at the time of installation. 6 figs.

  4. Asymmetric, stereodivergent synthesis of (-)-clusianone utilizing a biomimetic cationic cyclization.

    PubMed

    Boyce, Jonathan H; Porco, John A

    2014-07-21

    We report a stereodivergent, asymmetric total synthesis of (-)-clusianone in six steps from commercial materials. We implement a challenging cationic cyclization forging a bond between two sterically encumbered quaternary carbon atoms. Mechanistic studies point to the unique ability of formic acid to mediate the cyclization forming the clusianone framework. PMID:24916169

  5. Interactions of Monovalent Organic Cations with Pillared Clays.

    PubMed

    Mishael; Rytwo; Nir; Crespin; Annabi-Bergaya; Van Damme H

    1999-01-01

    Interactions between an acid-activated pillared clay and several organic cations including dyes (methylene blue, MB; crystal violet, CV; acriflavin, AF) and benzyl derivatives (benzyltrimethylammonium, BTMA; benzyltriethylammonium, BTEA) were studied by adsorption measurements and X-ray diffraction. When the dyes were adsorbed from low ionic strength solutions, adsorption was irreversible but saturated at levels below the cation exchange capacity (CEC) of the clay (0.6 meq/g). The difference with CEC value was largest for CV. This mode of adsorption was interpreted in terms of interlayer adsorption with steric hindrance in the pillared galleries. On the other hand, when the dyes were adsorbed from high ionic strength solutions, adsorption levels well beyond the CEC of the clay could be reached, in particular for MB and CV. This was interpreted in terms of a second adsorption mode, involving formation of molecular aggregates on the outer surface of the clay, as evidenced by X-ray diffraction. The behavior of the cationic benzyl derivatives was markedly different, with an adsorption level always below the CEC and a decrease of adsorption as the ionic strength was increased, as expected for non-complex-forming cations. Copyright 1999 Academic Press. PMID:9878144

  6. A cationic gold complex cleaves BArF24.

    PubMed

    Weber, Simone G; Zahner, David; Rominger, Frank; Straub, Bernd F

    2012-11-28

    A sterically shielded cationic NHC gold complex IPr**Au-BArF(24) without solvent coordination has been prepared in situ in CH(2)Cl(2). The monovalent transition metal electrophile, a "soft proton", heterolytically activates the C-B bond of the weakly coordinating counterion tetrakis[3,5-bis(trifluoromethyl)phenyl]borate at room temperature. PMID:23073224

  7. Cu Vacancies Boost Cation Exchange Reactions in Copper Selenide Nanocrystals

    PubMed Central

    2015-01-01

    We have investigated cation exchange reactions in copper selenide nanocrystals using two different divalent ions as guest cations (Zn2+ and Cd2+) and comparing the reactivity of close to stoichiometric (that is, Cu2Se) nanocrystals with that of nonstoichiometric (Cu2–xSe) nanocrystals, to gain insights into the mechanism of cation exchange at the nanoscale. We have found that the presence of a large density of copper vacancies significantly accelerated the exchange process at room temperature and corroborated vacancy diffusion as one of the main drivers in these reactions. Partially exchanged samples exhibited Janus-like heterostructures made of immiscible domains sharing epitaxial interfaces. No alloy or core–shell structures were observed. The role of phosphines, like tri-n-octylphosphine, in these reactions, is multifaceted: besides acting as selective solvating ligands for Cu+ ions exiting the nanoparticles during exchange, they also enable anion diffusion, by extracting an appreciable amount of selenium to the solution phase, which may further promote the exchange process. In reactions run at a higher temperature (150 °C), copper vacancies were quickly eliminated from the nanocrystals and major differences in Cu stoichiometries, as well as in reactivities, between the initial Cu2Se and Cu2–xSe samples were rapidly smoothed out. These experiments indicate that cation exchange, under the specific conditions of this work, is more efficient at room temperature than at higher temperature. PMID:26140622

  8. Cationic Polymerization of Vegetable Oils in Supercritical Carbon Dioxide

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Polymers derived from vegetable oils have been prepared in supercritical carbon dioxide (scCO2) medium by cationic polymerization. Boron trifluoride diethyl etherate BF3.O(C2H2)2 are used as initiator. Influences of polymerization temperature, initiator amount, and carbon dioxide pressure on the m...

  9. Electron transfer reactions within zeolites: Radical cation from benzonorbornadiene

    SciTech Connect

    Pitchumani, K.; Ramamurthy, V.; Corbin, D.R.

    1996-08-28

    Zeolites are being used as solid acid catalysts in a number of commercial processes. Occasionally zeolites are also reported to perform as electron transfer agents. Recently, we observed that radical cations of certain olefins and thiophene oligomers can be generated spontaneously within ZSM-5 zeolites. We noticed that these radical cations generated from diphenyl polyenes and thiophene oligomers were remarkably stable (at room temperature) within ZSM-5 and can be characterized spectroscopically at leisure. We have initiated a program on electron transfer processes within large pore zeolites. The basis of this approach is that once a cation radical is generated within a large pore zeolite, it will have sufficient room to undergo a molecular transformation. Our aim is to identify a condition under which electron transfer can be routinely and reliably carried out within large pore zeolites such as faujasites. To our great surprise, when benzonorbornadiene A and a number of olefins were included in divalent cation exchanged faujasites. they were transformed into products very quickly (<15 min). This observation allowed us to explore the use of zeolites as oxidants. Results of our studies on benzonorbornadiene are presented in this communication. 16 refs., 1 fig.

  10. Fibrin solubilizing properties of certain anionic and cationic detergents.

    PubMed

    Chakrabarty, S

    1989-08-15

    The fibrinolytic (fibrin dissolving) properties of several anionic, cationic, nonionic and zwitterionic detergents were assessed in an in vitro fibrin agarose assay. Of the 4 anionic detergents tested, only sodium dodecyl sulfate (SDS) was found to be fibrinolytic. SDS was fibrinolytic either in the absence or presence of factor XIII. Four other cationic detergents were found to possess similar fibrinolytic properties. These cationic detergents were cetyltrimethylammonium bromide (CTAB), mix alkyltrimethyl ammonium bromide (MTAB), hexadecyltrimethylammonium bromide (HTAB) and cetylpyridium chloride (CPC). The nonionic (digitonin, triton X-100/tween 20) and zeitterionic (CHAPS, zeittergent 3-08) detergents were not fibrinolytic. Detergents mediated fibrinolysis, unlike that of tissue type plasminogen activator and urokinase, was independent of the presence of plasminogen. Non-detergents such as polyethylene glycol and highly charged compounds such as poly-1-lysine and poly-1-glutamic acid were not fibrinolytic. Fibrinolytic activity was observed for SDS and the cationic detergents at concentrations ranging from 0.1-10 percent. The effects of these fibrinolytic detergents (SDS, CTAB, MTAB, HTAB and CPC) on clot formation and on pre-formed clots were then assessed, using freshly drawn human venous blood. Incorporation of these detergents into blood inhibited the formation of clots in a concentration dependent manner. The detergents were also able to dissolve pre-formed clots in a similar fashion. SDS was found to be most potent in these properties. PMID:2510356

  11. Alloyed Copper Chalcogenide Nanoplatelets via Partial Cation Exchange Reactions

    PubMed Central

    2014-01-01

    We report the synthesis of alloyed quaternary and quinary nanocrystals based on copper chalcogenides, namely, copper zinc selenide–sulfide (CZSeS), copper tin selenide–sulfide (CTSeS), and copper zinc tin selenide–sulfide (CZTSeS) nanoplatelets (NPLs) (∼20 nm wide) with tunable chemical composition. Our synthesis scheme consisted of two facile steps: i.e., the preparation of copper selenide–sulfide (Cu2–xSeyS1–y) platelet shaped nanocrystals via the colloidal route, followed by an in situ cation exchange reaction. During the latter step, the cation exchange proceeded through a partial replacement of copper ions by zinc or/and tin cations, yielding homogeneously alloyed nanocrystals with platelet shape. Overall, the chemical composition of the alloyed nanocrystals can easily be controlled by the amount of precursors that contain cations of interest (e.g., Zn, Sn) to be incorporated/alloyed. We have also optimized the reaction conditions that allow a complete preservation of the size, morphology, and crystal structure as that of the starting Cu2–xSeyS1–y NPLs. The alloyed NPLs were characterized by optical spectroscopy (UV–vis–NIR) and cyclic voltammetry (CV), which demonstrated tunability of their light absorption characteristics as well as their electrochemical band gaps. PMID:25050455

  12. Quality control of cationic cell-penetrating peptides.

    PubMed

    Stalmans, Sofie; Gevaert, Bert; Verbeke, Frederick; D'Hondt, Matthias; Bracke, Nathalie; Wynendaele, Evelien; De Spiegeleer, Bart

    2016-01-01

    During fundamental research, it is recommended to evaluate the test compound identity and purity in order to obtain reliable study outcomes. For peptides, quality control (QC) analyses are routinely performed using reversed-phase liquid chromatography coupled to an ultraviolet (UV) detector system. These traditional QC methods, using a C18 column and a linear gradient with formic acid (FA) as acidic modifier in the mobile phase, might not result in optimal chromatographic performance for basic peptides due to their cationic nature and hence may lead to erroneous results. Therefore, the influence of the used chromatographic system on the final QC results of basic peptides was evaluated using five cationic cell-penetrating peptides and five C18-chromatographic systems, differing in the column particle size (high performance liquid chromatography (HPLC) versus ultra-high performance liquid chromatography (UHPLC)), the acidic modifier (FA versus trifluoroacetic acid (TFA)), and the column temperature (30 °C versus 60 °C). Our results indicate that a UHPLC system with the C18 column thermostated at 30 °C and a mobile phase containing TFA, provides the most suitable routine QC analysis method for cationic peptides, outperforming in sensitivity and resolution compared to the other systems. We also demonstrate the use of a single quad mass spectrometry (MS) detector system during QC analysis of (cationic) peptides, allowing identification of the peptide and its impurities, as well as the evaluation of the peak purity. PMID:26397208

  13. Cationic zinc enolates as highly active catalysts for acrylate polymerization.

    PubMed

    Garner, Logan E; Zhu, Hongping; Hlavinka, Mark L; Hagadorn, John R; Chen, Eugene Y-X

    2006-11-22

    Unprecedented cationic zinc enolates have been generated by a novel activation route involving the amido to imino ligand transformation with B(C6F5)3, structurally characterized, and utilized as highly active catalysts for the production of high molecular weight polyacrylates at ambient temperature. PMID:17105289

  14. Cationic amphiphilic non-hemolytic polyacrylates with superior antibacterial activity.

    PubMed

    Punia, Ashish; He, Edward; Lee, Kevin; Banerjee, Probal; Yang, Nan-Loh

    2014-07-01

    Acrylic copolymers with appropriate compositions of counits having cationic charge with 2-carbon and 6-carbon spacer arms can show superior antibacterial activities with concomitant very low hemolytic effect. These amphiphilic copolymers represent one of the most promising synthetic polymer antibacterial systems reported. PMID:24854366

  15. Cation Hydration Constants by Proton NMR: A Physical Chemistry Experiment.

    ERIC Educational Resources Information Center

    Smith, Robert L.; And Others

    1988-01-01

    Studies the polarization effect on water by cations and anions. Describes an experiment to illustrate the polarization effect of sodium, lithium, calcium, and strontium ions on the water molecule in the hydration spheres of the ions. Analysis is performed by proton NMR. (MVL)

  16. Fly ash adsorbents for multi-cation wastewater treatment

    NASA Astrophysics Data System (ADS)

    Visa, Maria; Isac, Luminita; Duta, Anca

    2012-06-01

    Class "F" fly ash (FA), collected from the Central Heat and Power (CHP) Plant Brasov (Romania), with oxides composition SiO2/Al2O3 over 2.4 proved good adsorbent properties, and was further used for obtaining a new substrate with good adsorption capacity for heavy metals from multi-cation wastewater treatment. Firstly, the new adsorbent was characterized by AFM, XRD, DSC, FTIR and the surface energy was evaluated by contact angle measurements. The experimental data suggested that the new type of substrate is predominant crystalline with highly polar surface. The substrate was used for removing the Pb2+, Cd2+ and Zn2+ cations from mixed solutions. The results show high efficiency and selective adsorption the Pb2+ and Zn2+ cations. The optimized adsorption parameters were further used in thermodynamic and kinetic studies of the adsorption processes. The Langmuir and Freundlich models were used to describe the processes. The pseudo-second order kinetics could well model all the processes, indicating a surface concentration of the adsorption sites with the same order of magnitude as the cation concentrations.

  17. EFFECT OF CATIONS ON ALUMINUM SPECIATION UNDER ALKALINE CONDITIONS

    SciTech Connect

    Taylor-Pashow, K.; Hobbs, D.

    2012-07-31

    A series of experiments were performed to examine the effect of metal cations common to high level waste on the phase of aluminum formed. Experiments were performed at temperature of 150 C, 75 C, and room temperature, either without additional metal cation, or with 0.01-0.2 molar equivalents of either Ni{sup 2+}, Fe{sup 3+}, Mn{sup 2+}, or Cr{sup 3+}. Results showed that temperature has the greatest effect on the phase obtained. At 150 C, boehmite is the only phase obtained, independent of the presence of other metal cations, with only one exception where a small amount of gibbsite was also detected in the product when 0.2 equivalents of Ni{sup 2+} was present. At 75 C, a mixture of phases is obtained, most commonly including bayerite and gibbsite; however, boehmite is also formed under some conditions, including in the absence of additional metal ion. At room temperature, in the absence of additional metal ion, a mixture of bayerite and gibbsite is obtained. The addition of another metal cation suppresses the formation of gibbsite, with a couple of exceptions (0.2 equivalents of Ni{sup 2+} or 0.01 equivalents of Cr{sup 3+}) where both phases are still obtained.

  18. Photoinitiated cationic polymerization with multifunctional vinyl ether monomers

    SciTech Connect

    Cribello, J.V.; Lee, J.L.; Conlon, D.A.

    1983-01-01

    Until recently, multifunctional vinyl ether monomers have not been employed in UV curing applications. The recent discovery of diaryliodonium and triarylsulfonium salts as new classes of photoinitiators for cationic polylmerization has made it possible to formulate highly photosensitive UV curable coatings based on these monomers. The syntheses of these monomers and their reactivity as a function of their structure is reviewed and evaluated.

  19. Cu Vacancies Boost Cation Exchange Reactions in Copper Selenide Nanocrystals.

    PubMed

    Lesnyak, Vladimir; Brescia, Rosaria; Messina, Gabriele C; Manna, Liberato

    2015-07-29

    We have investigated cation exchange reactions in copper selenide nanocrystals using two different divalent ions as guest cations (Zn(2+) and Cd(2+)) and comparing the reactivity of close to stoichiometric (that is, Cu2Se) nanocrystals with that of nonstoichiometric (Cu(2-x)Se) nanocrystals, to gain insights into the mechanism of cation exchange at the nanoscale. We have found that the presence of a large density of copper vacancies significantly accelerated the exchange process at room temperature and corroborated vacancy diffusion as one of the main drivers in these reactions. Partially exchanged samples exhibited Janus-like heterostructures made of immiscible domains sharing epitaxial interfaces. No alloy or core-shell structures were observed. The role of phosphines, like tri-n-octylphosphine, in these reactions, is multifaceted: besides acting as selective solvating ligands for Cu(+) ions exiting the nanoparticles during exchange, they also enable anion diffusion, by extracting an appreciable amount of selenium to the solution phase, which may further promote the exchange process. In reactions run at a higher temperature (150 °C), copper vacancies were quickly eliminated from the nanocrystals and major differences in Cu stoichiometries, as well as in reactivities, between the initial Cu2Se and Cu(2-x)Se samples were rapidly smoothed out. These experiments indicate that cation exchange, under the specific conditions of this work, is more efficient at room temperature than at higher temperature. PMID:26140622

  20. An Improved Qualitative Analysis Procedure for Aluminum Subgroup Cations.

    ERIC Educational Resources Information Center

    Kistner, C. R.; Robinson, Patricia J.

    1983-01-01

    Describes a procedure for the qualitative analysis of aluminum subgroup cations designed to avoid failure to obtain lead or barium chromate precipitates or failure to report aluminum hydroxide when present (due to staining). Provides a flow chart and step-by-step explanation for the new procedure, indicating significantly improved student results.…

  1. Anxiogenic effects of generated ambient cations--a preliminary study

    SciTech Connect

    Giannini, A.J.; Jones, B.T.; Loiselle, R.H.; Price, W.A.

    1986-01-01

    The existence of the putative serotonin irritation syndrome (SIS) was tested in a human population. Volunteers were exposed to a highly cationized environment for two hours. Symptoms of anxiety and excitement significantly increased. During the time of exposure serum serotonin levels also increased significantly. These results support the existence of SIS as a clinical entity.

  2. 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.

  3. Weakly charged cationic nanoparticles induce DNA bending and strand separation.

    PubMed

    Railsback, Justin G; Singh, Abhishek; Pearce, Ryan C; McKnight, Timothy E; Collazo, Ramón; Sitar, Zlatko; Yingling, Yaroslava G; Melechko, Anatoli V

    2012-08-16

    Weakly charged cationic nanoparticles cause structural changes including local denaturing and compaction to DNA under mild conditions. The charged ligands bind to the phosphate backbone of DNA and the uncharged ligands penetrate the helix and disrupt base pairing. Mobility shifts in electrophoresis, molecular dynamics, and UV-vis spectrophotometry give clues to the details of the interactions. PMID:22711427

  4. Force Fields for Carbohydrate-Divalent Cation Interactions.

    PubMed

    Chen, Hsieh; Cox, Jason R; Panagiotopoulos, Athanassios Z

    2016-06-16

    We report molecular dynamics simulations to study intermolecular interactions for carbohydrate-divalent cation complexes. We observed that common force fields from literature with standard Lorentz-Berthelot combining rules are unable to reproduce the experimental stability constants for model carbohydrate monomer (α-d-Allopyranose) and alkali earth metal cation (Mg(2+), Ca(2+), Sr(2+), or Ba(2+)) complexes. A modified combining rule with rescaled effective cross-interaction radius between cations and the hydroxyl oxygens on the carbohydrates was introduced to reproduce the experimental stability constants, which the preferential carbohydrate-cation complexing structures through the ax-eq-ax sequence of O-1, O-2, and O-3 on α-d-Allopyranose were also observed. The effective radius scaling factor obtained from (α-d-Allopyranose)-Ca(2+) complexes was directly transferrable to the similar six-membered ring (α-d-Ribopyranose)-Ca(2+) complexes; however, reparameterization for the scaling factor may be necessary for the five-membered ring (α-d-Ribofuranose)-Ca(2+) complexes. PMID:27210229

  5. 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)

  6. Electrical conductivity in two mixed-valence liquids.

    PubMed

    Yao, Wenzhi; Kelley, Steven P; Rogers, Robin D; Vaid, Thomas P

    2015-06-01

    Two different room-temperature liquid systems were investigated, both of which conduct a DC electrical current without decomposition or net chemical transformation. DC electrical conductivity is possible in both cases because of the presence of two different oxidation states of a redox-active species. One system is a 1 : 1 molar mixture of n-butylferrocene (BuFc) and its cation bis(trifluoromethane)sulfonimide salt, [BuFc(+)][NTf2(-)], while the other is a 1 : 1 molar mixture of TEMPO and its cation bis(trifluoromethane)sulfonimide salt, [TEMPO(+)][NTf2(-)]. The TEMPO-[TEMPO(+)][NTf2(-)] system is notable in that it is an electrically conducting liquid in which the conductivity originates from an organic molecule in two different oxidation states, with no metals present. Single-crystal X-ray diffraction of [TEMPO(+)][NTf2(-)] revealed a complex structure with structurally different cation-anion interactions for cis- and trans [NTf2(-)] conformers. The electron transfer self-exchange rate constant for BuFc/BuFc(+) in CD3CN was determined by (1)H NMR spectroscopy to be 5.4 × 10(6) M(-1) s(-1). The rate constant allowed calculation of an estimated electrical conductivity of 7.6 × 10(-5)Ω(-1) cm(-1) for BuFc-[BuFc(+)][NTf2(-)], twice the measured value of 3.8 × 10(-5)Ω(-1) cm(-1). Similarly, a previously reported self-exchange rate constant for TEMPO/TEMPO(+) in CH3CN led to an estimated conductivity of 1.3 × 10(-4)Ω(-1) cm(-1) for TEMPO-[TEMPO(+)][NTf2(-)], a factor of about 3 higher than the measured value of 4.3 × 10(-5)Ω(-1) cm(-1). PMID:25960288

  7. Thermal conductivity of model zeolites: molecular dynamics simulation study

    NASA Astrophysics Data System (ADS)

    Murashov, Vladimir V.

    1999-02-01

    The thermal conductivity of model zeolites was investigated using non-equilibrium molecular dynamics calculations. This type of calculation was found to overestimate the thermal conductivity of low-density silica polymorphs. A better reproduction of the experimental results was found for zeolites, and this was related to the lower phonon mean free path. The thermal conductivity of framework silicates was shown to be determined primarily by the vibrations of the continuous oxygen sublattice. Thus, the most drastic suppression of the heat transfer was related to alterations of the O-O distances; for example, a sixfold reduction in thermal conductivity compared to that of siliceous LTA zeolite was found for LTA-A1PO4. Framework cations were shown to affect the heat transfer by changing the vibrational modes of the structural building units of the framework and non-framework counter-cations, by disturbing the oxygen sublattice locally and acting as Rayleigh and resonant scatterers. A model assuming the heat transfer to be due only to non-dispersive acoustic phonons failed to reproduce the dependence of the thermal conductivity on the mass of the cations and the unit-cell dimension, thus suggesting a more sophisticated mechanism of heat transfer to be operative in framework materials. The effect of non-framework non-ionic species on the thermal conductivity was shown to be determined by their effect on the characteristics of the oxygen framework vibrations. Thus, repulsive interactions between the oxygen sublattice and Xe8 clusters, reducing the anisotropy and anharmonicity of the oxygen vibrations, give rise to enhanced heat transfer in LTA-SiO2 at ambient conditions.

  8. Electrically conductive cellulose composite

    DOEpatents

    Evans, Barbara R.; O'Neill, Hugh M.; Woodward, Jonathan

    2010-05-04

    An electrically conductive cellulose composite includes a cellulose matrix and an electrically conductive carbonaceous material incorporated into the cellulose matrix. The electrical conductivity of the cellulose composite is at least 10 .mu.S/cm at 25.degree. C. The composite can be made by incorporating the electrically conductive carbonaceous material into a culture medium with a cellulose-producing organism, such as Gluconoacetobacter hansenii. The composites can be used to form electrodes, such as for use in membrane electrode assemblies for fuel cells.

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

    NASA Astrophysics Data System (ADS)

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

    2005-10-01

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

  10. Solubilization of pentanol by cationic surfactants and binary mixtures of cationic surfactants

    SciTech Connect

    Morgan, M.E.

    1993-12-31

    The research reported here has included studies of the solubilization of pentanol in hexadecylpyridinium chloride (CPC), trimethyletetradecylammonium chloride (C{sub 14}Cl), benzyldimethyltetradecylammonium chloride (C{sub 14}BzCl), benzyldimethylhexadecylpyridinium chloride (C{sub 16}BzCl), hexadecyltrimethylammonium bromide (CTAB), and binary mixtures of CPC + C{sub 16}BzCl and C{sub 14}Cl + C{sub 14}BzCl. Rather than using calorimetric methods, this project will employ headspace chromatography to measure solubilization of pentanol over a wide range of solute concentrations. While not yielding as much thermodynamic data as calorimetry, headspace chromatography is a more direct measure of the extent of solubilization. Using headspace chromatography, is a more direct measure of the extent of solubilization. Using headspace chromatography, this study will seek to determine whether strongly synergistic mixture ratios exist in the case of binary cationic surfactant systems. There are two equilibria in the pentanol-water-surfactant system: (1) The pentanol solubilized in micelles is in equilibrium with the monomeric pentanol in solution, and (2) the monomeric pentanol is in equilibrium with the pentanol in the vapor above the solution. To establish the link between the two equilibria, a sample of the vapor above pure liquid pentanol must be collected, in order to find the activity of pentanol in solution. Also, a calibration curve for various concentrations of pentanol in solution. From this type of data it is possible to infer both the concentration of pentanol solubilized in micelles and the concentrations of pentanol in the ``bulk`` solution outside the micelles. The method is equally applicable to systems containing a single surfactant as well as mixtures of surfactants.

  11. Photo-fragmentation spectroscopy of benzylium and 1-phenylethyl cations

    SciTech Connect

    Féraud, Géraldine; Dedonder-Lardeux, Claude; Jouvet, Christophe; Soorkia, Satchin

    2014-01-14

    The electronic spectra of cold benzylium (C{sub 6}H{sub 5}-CH{sub 2}{sup +}) and 1-phenylethyl (C{sub 6}H{sub 5}-CH-CH{sub 3}{sup +}) cations have been recorded via photofragment spectroscopy. Benzylium and 1-phenylethyl cations produced from electrosprayed benzylamine and phenylethylamine solutions, respectively, were stored in a cryogenically cooled quadrupole ion trap and photodissociated by an OPO laser, scanned in parts of the UV and visible regions (600–225 nm). The electronic states and active vibrational modes of the benzylium and 1-phenylethyl cations as well as those of their tropylium or methyl tropylium isomers have been calculated with ab initio methods for comparison with the spectra observed. Sharp vibrational progressions are observed in the visible region while the absorption features are much broader in the UV. The visible spectrum of the benzylium cation is similar to that obtained in an argon tagging experiment [V. Dryza, N. Chalyavi, J. A. Sanelli, and E. J. Bieske, J. Chem. Phys. 137, 204304 (2012)], with an additional splitting assigned to Fermi resonances. The visible spectrum of the 1-phenylethyl cation also shows vibrational progressions. For both cations, the second electronic transition is observed in the UV, around 33 000 cm{sup −1} (4.1 eV) and shows a broadened vibrational progression. In both cases the S{sub 2} optimized geometry is non-planar. The third electronic transition observed around 40 000 cm{sup −1} (5.0 eV) is even broader with no apparent vibrational structures, which is indicative of either a fast non-radiative process or a very large change in geometry between the excited and the ground states. The oscillator strengths calculated for tropylium and methyl tropylium are weak. Therefore, these isomeric structures are most likely not responsible for these absorption features. Finally, the fragmentation pattern changes in the second and third electronic states: C{sub 2}H{sub 2} loss becomes predominant at higher

  12. Cation reordering in natural titanomagnetites and implications for paleointensity studies

    NASA Astrophysics Data System (ADS)

    Bowles, J. A.; Jackson, M. J.; Gee, J. S.

    2013-05-01

    Successful paleointensity experiments hinge on the underlying assumption of reciprocity; the remanence acquired over a particular temperature range should be fully removed over the same temperature range, and vice versa. This means that the blocking (TB) and unblocking (TUB) temperature spectra are identical and do not change during the course of the experiment. We will present the results of recent work demonstrating that some natural titanomagnetites undergo cation reordering on laboratory timescales and at temperatures at or below the Curie temperature (TC). The bulk composition of the titanomagnetites (Fe3-xTixO4) varies between approximately 0.2 < x < 0.4, with moderate degrees of Mg and Al substitution. Although there is no attendant structural or chemical alteration, the re-distribution of ferric and ferrous iron cations results in reversible changes in Curie temperature of up to 150°C. This necessarily changes the blocking temperature spectrum as a function of prior thermal history. These changes in TC, TUB and TB clearly pose problems for all paleointensity experiments, but the effects may be most apparent during Thellier-type experiments where the sample is step-wise heated to increasingly higher temperatures. The blocking temperature distribution will be expected to change over the course of the experiment even in the absence of chemical alteration, and one can expect the experiment to fail. We will explore the effects of cation redistribution on paleointensity experiments through numerical models and by comparison with paleointensity data from pumice samples taken from the 1980 pyroclastic flows at Mt. St. Helens (MSH). In the MSH samples, two phases are typically present: a predominantly multi-domain, homogeneous titanomagnetite (associated with the cation reordering) and an oxyexsolved, single-domain to pseudo-single-domain phase with ilmenite lamellae in a magnetite-rich host. Samples that result in technically successful paleointensity experiments

  13. Fluorescence quenching of water-soluble conjugated polymer by metal cations and its application in sensor

    NASA Astrophysics Data System (ADS)

    Chen, Yan-Guo; Zhao, Dan; He, Zhi-Ke; Ai, Xin-Ping

    2007-02-01

    The effects of different metal cations on the fluorescence of water-soluble conjugated polymer (CP) and their quenching mechanism have been explored. Most transition metal cations, especially noble metal cations, such as Pd 2+, Ru 3+, and Pt 2+ possessed higher quenching efficiency to CP fluorescence than that of the main group metal cations and other transition metal cations, which have filled or half-full outmost electron layer configurations. Base on this, rapid, sensitive detection of noble metal cations can be realized and a novel quencher-tether-ligand (QTL) probe was developed to detect avidin and streptavidin.

  14. β-Alaninium tetrafluoroborate: a new salt with di-β-alaninium dimeric cation.

    PubMed

    Ghazaryan, V V; Fleck, M; Petrosyan, A M

    2015-07-01

    β-Alaninium tetrafluoroborate crystallizes in the monoclinic system (space group P21/n, Z=4). The asymmetric unit contains one β-alaninium cation and one tetrafluoroborate anion, in which the fluorine atoms are disordered. All β-alaninium cations are connected with the symmetry related cations via an inversion center, thus forming dimeric centrosymmetric β-Ala(+)···β-Ala(+) cations. The O···O distance (2.698(2)Å) in the dimeric cation is relatively long compared to known distances of previously reported salts with A(+)···A(+) type dimeric cations. The infrared and Raman spectra are studied. PMID:25813178

  15. Voltage Regulation of Connexin Channel Conductance

    PubMed Central

    Oh, Seunghoon

    2015-01-01

    Voltage is an important parameter that regulates the conductance of both intercellular and plasma membrane channels (undocked hemichannels) formed by the 21 members of the mammalian connexin gene family. Connexin channels display two forms of voltage-dependence, rectification of ionic currents and voltage-dependent gating. Ionic rectification results either from asymmetries in the distribution of fixed charges due to heterotypic pairing of different hemichannels, or by channel block, arising from differences in the concentrations of divalent cations on opposite sides of the junctional plaque. This rectification likely underpins the electrical rectification observed in some electrical synapses. Both intercellular and undocked hemichannels also display two distinct forms of voltage-dependent gating, termed Vj (fast)-gating and loop (slow)-gating. This review summarizes our current understanding of the molecular determinants and mechanisms underlying these conformational changes derived from experimental, molecular-genetic, structural, and computational approaches. PMID:25510741

  16. Cuprous Ion Conducting Montmorillonite- Polypyrrole Nanocomposites

    NASA Astrophysics Data System (ADS)

    Krishantha, D. M. M.; Rajapakse, R. M. G.; Tennakoon, D. T. B.; Bandara, W. M. A. T.; Thilakarathna, P. N. L.

    2006-06-01

    Solid state polymer-Silicate nanocomposite based on Polypyrrole-Cu+-montmorilonite were prepared and electrical properties were investigated. In this preparation, Na-montmorillonite (Na+-MMT) was purified by repeated washing with distilled water and the intergallery cations were exchanged for Cu(II). The cupric ions exchanged-MMT(Cu(II)-- MMT) was again exposed to pyrrole in aqueous acidic solution to yield polypyrrole-Cu+-MMT nanocomposite. DC polarization test and AC impedance measurement reveal that the materials are mixed conductors. The ionic conductivity is due to the motion of cuprous ions which is facilitated by microstructure of polypyrrrole present in the intergalleries. An electrochemical cell was fabricated using the materials which can be represented by Cu(s)/ Cu+-PPY-MMT/Cu2SO4 (s)/Na2SO4(S)-Na2S2O8(s)/ and gave a 1.00 V. The cell is rechargeable.

  17. Rectification of the Channelrhodopsin Early Conductance

    PubMed Central

    Gradmann, Dietrich; Berndt, André; Schneider, Franziska; Hegemann, Peter

    2011-01-01

    We analyzed the nonlinear current-voltage relationships of the early conducting state of channelrhodopsin-2 expressed in Xenopus oocytes and human embryonic kidney cells with respect to changes of the electrochemical gradients of H+, Na+/K+, and Ca2+/Mg2+. Several models were tested for wild-type ChR2 and mutations at positions E90, E123, H134, and T159. Voltage-gating was excluded as cause for the nonlinearity. However, a general enzyme kinetic model with one predominant binding site yielded good fits throughout. The empty site with an apparent charge number of about −0.3 and strong external cation binding causes some inward rectification of the uniport function. Additional inward rectification is due to asymmetric competition from outside between the transported ion species. Significant improvement of the fits was achieved by introducing an elastic voltage-divider formed by the voltage-sensitive barriers. PMID:21889442

  18. Microemulsion formation and phase behavior of anionic and cationic surfactants with sodium dodecyl sulfate and cetyltrimethylammonium bromide

    SciTech Connect

    Li, X.; Lin, E.; Zhao, G.; Xiao, T.

    1996-12-01

    The phase behavior and solubilization of multiphase microemulsions in mixed anionic-cationic surfactant systems were studied for fixed ratio of water-to-oil and surfactant-to-alcohol. In the mixed surfactants (sodium dodecyl sulfate + cetyltrimethylammonium bromide)/heptane/alcohol/water systems, microemulsions and birefringement phases are formed by adjusting the surfactant ratio {epsilon} and the cationic weight fraction {delta}. The bicontinuous (or w/o microemulsion) {yields} birefringement o/w microemulsion transition takes place and microemulsion domain enlarges with increasing {epsilon}. The optimum surfactant concentration {gamma} increases and the corresponding optimum {delta} decreases with increasing {epsilon} and both of them decrease with increasing the alcohol chain length butanol to hexanol. The birefringent region shrinks rapidly with increasing alcohol and/or CTAB weight fractions in total surfactant concentration. Conductivity measurements have been performed in the single-phase region of the system containing mixed surfactants and alcohols at 25 C. The conductivity results indicate where a transition takes place and which of these different types of phase structures may be in the single-phase of the system containing anionic-cationic mixed surfactants.

  19. Combinatorial Study of Ag-Te Thin Films and Their Application as Cation Supply Layer in CBRAM Cells.

    PubMed

    Devulder, Wouter; Opsomer, Karl; Meersschaut, Johan; Deduytsche, Davy; Jurczak, Malgorzata; Goux, Ludovic; Detavernier, Christophe

    2015-05-11

    In this work, we investigate binary Ag-Te thin films and their functionality as a cation supply layer in conductive bridge random access memory devices. A combinatorial sputter deposition technique is used to deposit a graded Ag(x)Te(1-x) (0 < x < 1) layer with varying composition as a function of the position on the substrate. The crystallinity, surface morphology, and material stability under thermal treatment as a function of the composition of the material are investigated. From this screening, a narrow composition range between 33 and 38 at% Te is selected which shows a good morphology and a high melting temperature. Functionality of a single Ag(2-δ)Te composition as cation supply layer in CBRAM with dedicated Al2O3 switching layer is then investigated by implementing it in 580 μm diameter dot Pt/Ag(2-δ)Te/Al2O3/Si cells. Switching properties are investigated and compared to cells with a pure Ag cation supply layer. An improved cycling behavior is observed when Te is added compared to pure Ag, which we relate to the ionic conducting properties of Ag2Te and the preferred formation of Ag-Te phases. PMID:25860668

  20. Osteoblast response to hydroxyapatite doped with divalent and trivalent cations.

    PubMed

    Webster, Thomas J; Massa-Schlueter, Elizabeth A; Smith, Jennifer L; Slamovich, Elliot B

    2004-05-01

    The present in vitro study doped hydroxyapatite (HA) with various metal cations (Mg(2+), Zn(2+), La(3+), Y(3+), In(3+), and Bi(3+)) in an attempt to enhance properties of HA pertinent to orthopedic and dental applications. X-ray diffraction material characterization indicated that the metal cations may have substituted for calcium in the HA crystal structure and that all of the doped HA formulations were single-phase and crystalline. Scanning electron microscopy analysis revealed a variety of grain sizes, depending on the dopant utilized. Energy-dispersive spectroscopy confirmed that the dopants added during synthesis were present and that all of the HA formulations synthesized were within the defined range of HA phase in the CaO-P(2)O(5)-H(2)O system. Lastly, Bi-doped HA had a slower dissolution rate than either undoped HA or HA doped with other cations when exposed to simulated physiological conditions for 21 days. In terms of cell function, results provided the first evidence that osteoblasts, bone-forming cells, adhered and differentiated (as measured by alkaline phosphatase synthesis) in response to HA doped with trivalent cations (specifically, La(3+), Y(3+), In(3+), Bi(3+)) at earlier time points than either HA doped with divalent cations (Mg(2+), Zn(2+)) or undoped HA. Of the dopants examined, Bi(3+) most enhanced osteoblast long-term calcium-containing mineral deposition. For these reasons, this study revealed for the first time the potential benefits of doping HA with Bi(3+) according to criteria critical for bone prosthetic clinical success. PMID:14741626

  1. Electronically and ionically conductive porous material and method for manufacture of resin wafers therefrom

    DOEpatents

    Lin, YuPo J.; Henry, Michael P.; Snyder, Seth W.

    2011-07-12

    An electrically and ionically conductive porous material including a thermoplastic binder and one or more of anion exchange moieties or cation exchange moieties or mixtures thereof and/or one or more of a protein capture resin and an electrically conductive material. The thermoplastic binder immobilizes the moieties with respect to each other but does not substantially coat the moieties and forms the electrically conductive porous material. A wafer of the material and a method of making the material and wafer are disclosed.

  2. Electronically and ionically conductive porous material and method for manufacture of resin wafers therefrom

    DOEpatents

    Lin, YuPo J.; Henry, Michael P.; Snyder, Seth W.

    2008-11-18

    An electrically and ionically conductive porous material including a thermoplastic binder and one or more of anion exchange moieties or cation exchange moieties or mixtures thereof and/or one or more of a protein capture resin and an electrically conductive material. The thermoplastic binder immobilizes the moieties with respect to each other but does not substantially coat the moieties and forms the electrically conductive porous material. A wafer of the material and a method of making the material and wafer are disclosed.

  3. Electrical conductivity measurements on silicate melts using the loop technique

    NASA Technical Reports Server (NTRS)

    Waff, H. S.

    1976-01-01

    A new method is described for measurement of the electrical conductivity of silicate melts under controlled oxygen partial pressure at temperatures to 1550 C. The melt samples are suspended as droplets on platinum-rhodium loops, minimizing iron loss from the melt due to alloying with platinum, and providing maximum surface exposure of the melt to the oxygen-buffering gas atmosphere. The latter provides extremely rapid equilibration of the melt with the imposed oxygen partial pressure. The loop technique involves a minimum of setup time and cost, provides reproducible results to within + or - 5% and is well suited to electrical conductivity studies on silicate melts containing redox cations.

  4. Codes of Conduct

    ERIC Educational Resources Information Center

    Million, June

    2004-01-01

    Most schools have a code of conduct, pledge, or behavioral standards, set by the district or school board with the school community. In this article, the author features some schools that created a new vision of instilling code of conducts to students based on work quality, respect, safety and courtesy. She suggests that communicating the code…

  5. Electrically conductive diamond electrodes

    DOEpatents

    Swain, Greg; Fischer, Anne ,; Bennett, Jason; Lowe, Michael

    2009-05-19

    An electrically conductive diamond electrode and process for preparation thereof is described. The electrode comprises diamond particles coated with electrically conductive doped diamond preferably by chemical vapor deposition which are held together with a binder. The electrodes are useful for oxidation reduction in gas, such as hydrogen generation by electrolysis.

  6. Conductive Critical Thinking

    ERIC Educational Resources Information Center

    Paetkau, Mark

    2007-01-01

    One of my goals as an instructor is to teach students critical thinking skills. This paper presents an example of a student-led discussion of heat conduction at the first-year level. Heat loss from a human head is calculated using conduction and radiation models. The results of these plausible (but wrong) models of heat transfer contradict what…

  7. Conductive Education Evaluated.

    ERIC Educational Resources Information Center

    Stukat, Karl Gustav

    1995-01-01

    This paper evaluates two research projects concerned with conductive education for children with cerebral palsy, one in Germany and the other in the United Kingdom. Issues of generalizability and drawing causal conclusions are raised. The paper finds that neither the most sanguine expectations nor the worst misgivings about conductive education…

  8. Atomic-scale imaging of cation ordering in inverse spinel Zn2SnO4 nanowires.

    PubMed

    Bao, Lihong; Zang, Jianfeng; Wang, Guofeng; Li, Xiaodong

    2014-11-12

    By using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) coupled with density functional theory (DFT) calculations, we demonstrate the atomic-level imaging of cation ordering in inverse spinel Zn2SnO4 nanowires. This cation ordering was identified as 1:1 ordering of Zn(2+) and Sn(4+) at the octahedral sites of the inverse spinel crystal with microscopic symmetry transition from original cubic Fd3̅m to orthorhombic Imma group. This ordering generated a 67.8% increase in the elastic modulus and 1-2 order of magnitude lower in the electric conductivity and electron mobility compared to their bulk counterpart. PMID:25300009

  9. Cationic Membrane Peptides: Atomic-Level Insight of Structure-Activity Relationships from Solid-State NMR

    PubMed Central

    Su, Yongchao; Li, Shenhui; Hong, Mei

    2012-01-01

    Many membrane-active peptides, such as cationic cell-penetrating peptides (CPPs) and antimicrobial peptides (AMPs), conduct their biological functions by interacting with the cell membrane. The interactions of charged residues with lipids and water facilitate membrane insertion, translocation or disruption of these highly hydrophobic species. In this mini-review we will summarize high-resolution structural and dynamic findings towards the understanding of the structure-activity relationship of lipid membrane-bound CPPs and AMPs, as examples of the current development of solid-state NMR (SSNMR) techniques for studying membrane peptides. We will present the most recent atomic-resolution structure of the guanidinium-phosphate complex, as constrained from experimentally measured site-specific distances. These SSNMR results will be valuable specifically for understanding the intracellular translocation pathway of CPPs and antimicrobial mechanism of AMPs, and more generally broaden our insight into how cationic macromolecules interact with and cross the lipid membrane. PMID:23108593

  10. Prevention of cardiolipin oxidation and fatty acid cycling as two antioxidant mechanisms of cationic derivatives of plastoquinone (SkQs).

    PubMed

    Skulachev, Vladimir P; Antonenko, Yury N; Cherepanov, Dmitry A; Chernyak, Boris V; Izyumov, Denis S; Khailova, Ludmila S; Klishin, Sergey S; Korshunova, Galina A; Lyamzaev, Konstantin G; Pletjushkina, Olga Yu; Roginsky, Vitaly A; Rokitskaya, Tatiana I; Severin, Fedor F; Severina, Inna I; Simonyan, Ruben A; Skulachev, Maxim V; Sumbatyan, Natalia V; Sukhanova, Evgeniya I; Tashlitsky, Vadim N; Trendeleva, Tatyana A; Vyssokikh, Mikhail Yu; Zvyagilskaya, Renata A

    2010-01-01

    The present state of the art in studies on the mechanisms of antioxidant activities of mitochondria-targeted cationic plastoquinone derivatives (SkQs) is reviewed. Our experiments showed that these compounds can operate as antioxidants in two quite different ways, i.e. (i) by preventing peroxidation of cardiolipin [Antonenko et al., Biochemistry (Moscow) 73 (2008) 1273-1287] and (ii) by fatty acid cycling resulting in mild uncoupling that inhibits the formation of reactive oxygen species (ROS) in mitochondrial State 4 [Severin et al. Proc. Natl. Acad. Sci. USA 107 (2009), 663-668]. The quinol and cationic moieties of SkQ are involved in cases (i) and (ii), respectively. In case (i) SkQH2 interrupts propagation of chain reactions involved in peroxidation of unsaturated fatty acid residues in cardiolipin, the formed SkQ- being reduced back to SkQH2 by heme bH of complex III in an antimycin-sensitive way. Molecular dynamics simulation showed that there are two stable conformations of SkQ1 with the quinol residue localized near peroxyl radicals at C9 or C13 of the linoleate residue in cardiolipin. In mechanism (ii), fatty acid cycling mediated by the cationic SkQ moiety is involved. It consists of (a) transmembrane movement of the fatty acid anion/SkQ cation pair and (b) back flows of free SkQ cation and protonated fatty acid. The cycling results in a protonophorous effect that was demonstrated in planar phospholipid membranes and liposomes. In mitochondria, the cycling gives rise to mild uncoupling, thereby decreasing membrane potential and ROS generation coupled to reverse electron transport in the respiratory chain. In yeast cells, dodecyltriphenylphosphonium (capital ES, Cyrillic12TPP), the cationic part of SkQ1, induces uncoupling that is mitochondria-targeted since capital ES, Cyrillic12TPP is specifically accumulated in mitochondria and increases the H+ conductance of their inner membrane. The conductance of the outer cell membrane is not affected by capital ES

  11. Conductive fabric seal

    DOEpatents

    Livesay, Ronald Jason; Mason, Brandon William; Kuhn, Michael Joseph; Rowe, Nathan Carl

    2015-10-13

    Disclosed are several examples of a system and method for detecting if an article is being tampered with. Included is a covering made of a substrate that is coated with a layer of an electrically conductive material that forms an electrically conductive surface having an electrical resistance. The covering is configured to at least partially encapsulate the article such that the article cannot be tampered with, without modifying the electrical resistance of the electrically conductive surface of the covering. A sensing device is affixed to the electrically conductive surface of the covering and the sensing device monitors the condition of the covering by producing a signal that is indicative of the electrical resistance of the electrically conductive surface of the covering. A measured electrical resistance that differs from a nominal electrical resistance is indicative of a covering that is being tampered with and an alert is communicated to an observer.

  12. Electrical conductivity of iron-bearing silicate glasses and melts. Implications for the mechanisms of iron redox reactions

    NASA Astrophysics Data System (ADS)

    Malki, M.; Magnien, V.; Pinet, O.; Richet, P.

    2015-09-01

    The electrical conductivity of a series of glasses and melts of the system SiO2-CaO-MgO-M2O-"FeO" (M = Li and Na) and of a borosilicate has been measured from room temperature to about 1820 K. For samples with predominantly reduced iron, the conductivity increases markedly upon addition of Na+ and still more of Li+, which is consistent with the increasing order Mg2+, Na+, Li+ order of cation mobility. For the oxidized samples the conductivity is in contrast almost not affected by the presence of alkali cations, which agrees with the low mobility of alkali cations that are then serving as charge compensators of tetrahedrally coordinated Al3+. The conductivity is higher for oxidized than for reduced samples. As indicated by polarization electrode phenomena and complementary continuous current measurements, this difference is due to an important contribution of electronic conduction caused by electronic charge transfer between iron species that exists in the oxidized samples. The diffusivities of oxygen and divalent cations were then determined from Eyring relationship and the measured conductivities, respectively and compared with the redox diffusivies determined for the same samples. The good agreement found between both kinds of data confirms the controlling role of divalent cations and of oxygen species in the redox kinetics near the glass transition and at high temperatures, respectively. In addition it illustrates that describing melt properties in an integrated manner is becoming possible.

  13. A Cationic Channel in the Guard Cell Tonoplast of Allium cepa.

    PubMed Central

    Amodeo, G.; Escobar, A.; Zeiger, E.

    1994-01-01

    Stomatal movements depend on an osmoregulation process in which swelling or shrinking of the guard cells opens or closes the stomatal pore. Ions and water fluxes are an essential aspect of guard cell osmoregulation. Thus far, studies of these fluxes have focused on the guard cell plasma membrane. Guard cells, however, are a multi-compartment system that includes a prominent vacuole, which has a primary role in turgor regulation. This study reports on a detailed characterization of an ion channel at the guard cell tonoplast of Allium cepa (onion). We used patch-clamp methodology with isolated tonoplast patches to study conduction and gating at the single channel level. A voltage-dependent outward-rectifying cationic channel (210 picosiemens) was the dominant conductance. In symmetrical solutions the channel displayed an ohmic behavior in its current-voltage relationship. It also showed a very large rectification in the open probability. The channel was predominantly cationic and its sequence of ionic selectivity was weak (Na+ > K+ > Rb+ > Cs+). The channel conductance was not affected by intravacuolar pH. Analysis of membrane patches with multiple channels showed that the probability of a channel to open was independent of the opening of the other channels present in the patch and that there was a conservation of the open probability for different channels. Ensemble records generated using a pulse protocol showed slow activation and deactivation kinetics. A first-latency analysis of single-channel records in response to protocols with different prepulse duration indicated that this channel has more than one closed state. PMID:12232260

  14. K(NpO(2))(3)(H(2)O)Cl(4): A channel structure assembled two- and three-center cation-cation interactions of neptunyl cations

    SciTech Connect

    Wang, Shuao; Alekseev, Evgeny V.; Depmeier, Wulf; Albrecht-Schmitt, Thomas E.

    2011-06-06

    A Np(V) compound containing three-center cation–cation interations, K(NpO₂)₃(H₂O)Cl₄, has been prepared by reacting Np(V) with KCl in molten boric acid. This compound forms a three-dimensional channel structure that is constructed from both two- and three-center cation–cation interactions. Three new bonding modes for cation–cation interactions are added to the summary of all known Np(V) compounds.

  15. Electrical properties of AC{sub 3}B{sub 4}O{sub 12}-type perovskite ceramics with different cation vacancies

    SciTech Connect

    Li, Guizhong; Chen, Zhi; Sun, Xiaojun; Liu, Laijun; Fang, Liang; Elouadi, Brahim

    2015-05-15

    Highlights: • AC{sub 3}B{sub 4}O{sub 12} perovskite with different concentration cation vacancies were prepared. • Cell parameter decreases with the increase of concentration of cation vacancies. • PTCO and CTO remain high dielectric permittivity but depress loss greatly. • Dielectric loss associates with cation vacancies and motion of oxygen vacancies. - Abstract: AC{sub 3}B{sub 4}O{sub 12}-type perovskite CaCu{sub 3}Ti{sub 4}O{sub 12} (CCTO), □{sub 0.34}Pr{sub 0.67}Cu{sub 3}Ti{sub 4}O{sub 12} (PCTO), □{sub 1}Cu{sub 3}Ta{sub 2}Ti{sub 2}O{sub 12} (CTTO), □{sub 2}Cu{sub 2}Ta{sub 4}O{sub 12} (CTO) ceramics with different concentration cation vacancies were prepared through traditional solid state reaction method. X-ray diffraction analysis indicated that CCTO and PCTO are perovskite cubic with space group Im-3 (no. 204) while CTTO and CTO are Pm-3 (no. 200). Cell parameter of the samples dramatically increases with the increase of cation vacancies. Dielectric permittivity of them maintains very high value of ∼10{sup 4} from room temperature to 550 K but the dielectric loss is depressed with the increase of cation vacancies in the same space group. The dielectric properties and conductivity behavior were described by the Debye relaxation and the universal dielectric response, respectively. The effect mechanism of cation vacancy and crystal structure on carrier transposition were discussed.

  16. First Cationic Uranyl-Organic Framework with Anion-Exchange Capabilities.

    PubMed

    Bai, Zhuanling; Wang, Yanlong; Li, Yuxiang; Liu, Wei; Chen, Lanhua; Sheng, Daopeng; Diwu, Juan; Chai, Zhifang; Albrecht-Schmitt, Thomas E; Wang, Shuao

    2016-07-01

    By controlling the extent of hydrolysis during the self-assembly process of a zwitterionic-based ligand with uranyl cations, we observed a structural evolution from the neutral uranyl-organic framework [(UO2)2(TTTPC)(OH)O(COOH)]·1.5DMF·7H2O (SCU-6) to the first cationic uranyl-organic framework with the formula of [(UO2)(HTTTPC)(OH)]Br·1.5DMF·4H2O (SCU-7). The crystal structures of SCU-6 and SCU-7 are layers built with tetranuclear and dinuclear uranyl clusters, respectively. Exchangeable halide anions are present in the interlaminar spaces balancing the positive charge of layers in SCU-7. Therefore, SCU-7 is able to effectively remove perrhenate anions from aqueous solution. Meanwhile, the H2PO4(-)-exchanged SCU-7 material exhibits a moderate proton conductivity of 8.70 × 10(-5) S cm(-1) at 50 °C and 90% relative humidity, representing nearly 80 times enhancement compared to the original material. PMID:27310580

  17. Stearylamine-Containing Cationic Nanoemulsion as a Promising Carrier for Gene Delivery.

    PubMed

    Silva, André L; Marcelino, Henrique R; Verissimo, Lourena M; Araujo, Ivonete B; Agnez-Lima, Lucymara F; do Egito, Eryvaldo S T

    2016-02-01

    The drawbacks related to the use of viral vectors in gene therapy have been stimulated the research in non-viral strategies such as cationic nanoemulsions. The aim of this work was to develop a stearylamine-containing nanoemulsion for gene therapy purpose. The formulation was chosen from a Pseudo-Ternary Phase Diagram and had its long-term stability assessed by Dynamic Light Scattering and Phase Analysis Light Scattering during 180 days at 4 degrees C, 25 degrees C and 40 degrees C. Besides, studies of sterilization and scale up of the product were conducted. It was demonstrated that the proposed system was stable up to 180 days when stored at 4 degrees C and could be sterilized by a 0.22 microm filter pore without changes on its characteristics. The scale up was possible by adjusting the volume to the sonication time. Because the nanoemulsion presented a droplet size smaller than 200 nm and a zeta potential higher than 30 mV, this system was able to correctly complex the plasmid model PIRES2-EGFP, as confirmed by the agarosis gel electrophoresis assay. The nanoemulsion toxicity evaluated over lung fetus human cells (MRC-5) was dose-dependent. However, it does not appear to be a limiting factor for further experiments aiming gene transfection. As a conclusion, stearylamine-containing cationic nanoemulsions can be used for gene therapy, since it presents suitable characteristics, stability and possibility of sterilization. PMID:27433584

  18. Structural disorder, anisotropic micro-strain and cation vacancies in thermo-electric lead chalcogenides.

    PubMed

    Christensen, Sebastian; Bindzus, Niels; Sist, Mattia; Takata, Masaki; Iversen, Bo Brummerstedt

    2016-06-21

    Thermoelectric materials can interconvert heat and electricity, and the extraordinary thermoelectric properties of lead chalcogenides (PbX, X = S, Se, Te) attract immense scientific interest. A key topic is the role of the cation in reaching a very low thermal conductivity necessary for efficient energy conversion. Here we present new structural insights about the deceptively simple rock-salt lead chalcogenides through a comparative multi-temperature synchrotron powder X-ray diffraction study. For the first time, the presence of anisotropic microstrain broadening as well as lead vacancies are quantified for all three compounds. The microstrain implies extended breakage of cubic symmetry as a sign of the incipient ferroelectric nature of PbX. The degree of microstrain is correlated to the transition pressure of a symmetry reducing phase transition, and this trend can be explained by anion mediated s-p hybridization on lead. The observed number of vacancies is greatest for PbS (4-8%), but two samples of PbS show different cation occupancy, and thus sample-dependent vacancies might be the property that unifies conflicting results reported for PbX. Gram-Charlier analysis identifies a local non-spherical distribution of Pb; however, model unbiased maximum entropy analysis indicates that any static displacement of Pb, if present, is less than 0.2 Å at 100 K. PMID:27240951

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

    SciTech Connect

    Derebe, Mehabaw G.; Sauer, David B.; Zeng, Weizhong; Alam, Amer; Shi, Ning; Jiang, Youxing

    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 the 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.

  20. Band gap engineering via electrostatic chemical strain in cation ordered LaSrAlO4

    NASA Astrophysics Data System (ADS)

    Balachandran, Prasanna V.; Rondinelli, James M.

    2014-03-01

    In this work, we employ density functional theory to examine a novel design route that employs A-site cation ordering to engineer the band gaps of (A,A')BO4 Ruddlesden-Popper (RP) oxides. Using LaSrAlO4 as a model material, we show that the band gap is highly sensitive to the A-site cation ordering ranging from 3-4.5 eV. When the [AlO2]-1 layers are interleaved between two chemically equivalent [LaO]1+ or [SrO]0+ layers, we obtain the smallest band gap with a reduction of ~1 eV determined from the Heyd, Scuseria, and Ernzerhof (HSE) hybrid exchange-correlation functional. We relate the observed band gap reduction to the local bond distortions arising from electrostatic chemical strain induced changes to the O 2 p and La 5 d states in the valence and conduction bands, respectively. The project was supported by The Defense Advanced Research Projects Agency (grant no. N66001-12-4224). The views, opinions, and/or findings reported here are solely those of the authors and do not represent official views of DARPA or DOD.

  1. Development of a fast capillary electrophoresis method to determine inorganic cations in biodiesel samples.

    PubMed

    Piovezan, Marcel; Costa, Ana Carolina O; Jager, Alessandra Vincenzi; de Oliveira, Marcone Augusto Leal; Micke, Gustavo Amadeu

    2010-07-19

    The aim of this study was to develop a fast capillary electrophoresis method for the determination of inorganic cations (Na(+), K(+), Ca(2+), Mg(2+)) in biodiesel samples, using barium (Ba(2+)) as the internal standard. The running electrolyte was optimized through effective mobility curves in order to select the co-ion and Peakmaster software was used to determine electromigration dispersion and buffer capacity. The optimum background electrolyte was composed of 10 mmol L(-1) imidazole and 40 mmol L(-1) of acetic acid. Separation was conducted in a fused-silica capillary (32 cm total length and 23.5 cm effective length, 50 microm I.D.), with indirect UV detection at 214 nm. The migration time was only 36 s. In order to obtain the optimized conditions for extraction, a fractional factorial experimental design was used. The variables investigated were biodiesel mass, pH, extractant volume, agitation and sonication time. The optimum conditions were: biodiesel mass of 200 mg, extractant volume of 200 microL and agitation of 20 min. The method is characterized by good linearity in the concentration range of 0.5-20 mg kg(-1) (r>0.999), limit of detection was equal to 0.3 mg kg(-1), inter-day precision was equal to 1.88% and recovery in the range of 88.0-120%. The developed method was successfully applied to the determination of cations in biodiesel samples. PMID:20599036

  2. Solubility and cation exchange in phosphate rock and saturated clinoptilolite mixtures

    NASA Technical Reports Server (NTRS)

    Allen, E. R.; Hossner, L. R.; Ming, D. W.; Henninger, D. L.

    1993-01-01

    Mixtures of zeolite and phosphate rock (PR) have the potential to provide slow-release fertilization of plants in synthetic soils by dissolution and ion-exchange reactions. This study was conducted to examine solubility and cation-exchange relationships in mixtures of PR and NH4- and K-saturated clinoptilolite (Cp). Batch-equilibration experiments were designed to investigate the effect of PR source, the proportion of exchangeable K and NH4, and the Cp to PR ratio on solution N, P, K, and Ca concentrations. The dissolution and cation-exchange reactions that occurred after mixing NH4- and K-saturated Cp with PR increased the solubility of the PR and simultaneously released NH4 and K into solution. The more reactive North Carolina (NC) PR rendered higher solution concentrations of NH4 and K when mixed with Cp than did Tennessee (TN) PR. Solution P concentrations for the Cp-NC PR mixture and the Cp-TN PR mixture were similar. Solution concentrations of N, P, K, and Ca and the ratios of these nutrients in solution varied predictably with the type of PR, the Cp/PR ratio, and the proportions of exchangeable K and NH4 on the Cp. Our research indicated that slow-release fertilization using Cp/PR media may provide adequate levels of N, P, and K to support plant growth. Solution Ca concentrations were lower than optimum for plant growth.

  3. Adsorption of heavy metal cations by Na-clinoptilolite: equilibrium and selectivity studies.

    PubMed

    Mihaly-Cozmuta, L; Mihaly-Cozmuta, A; Peter, A; Nicula, C; Tutu, H; Silipas, Dan; Indrea, Emil

    2014-05-01

    This paper summarizes the conclusions of experiments conducted on the adsorption of Cd(2+), Co(2+), Cu(2+), Mn(2+), Ni(2+), Pb(2+) and Zn(2+) onto zeolite. The focus of the experiments was to establish the influence of the initial pH of the contact solution as well as the selectivity of zeolite on the efficiency of the adsorption process. To this end, experimental adsorption isotherms were established for the pH values ranging from 1 to 4 by using the Na-form of clinoptilolite (particle size range 0.5-1 mm) as an adsorbent. Langmuir, Freundlich and Dubinin-Raduschkevich isotherm models were used to validate the experimental data and the Gibbs free energy was calculated based on the distribution coefficient. From the Langmuir model, correlations between the maximum adsorption capacity and selected physical-chemical parameters of the cations studied were established. The results of the experiments suggest that the selectivity of zeolite is strongly influenced by the pH of the contact solution, dehydration energy of cations, diffusion coefficient and the pH at which the precipitation of hydroxides occurs. PMID:24603029

  4. Light-induced cation exchange for copper sulfide based CO2 reduction.

    PubMed

    Manzi, Aurora; Simon, Thomas; Sonnleitner, Clemens; Döblinger, Markus; Wyrwich, Regina; Stern, Omar; Stolarczyk, Jacek K; Feldmann, Jochen

    2015-11-11

    Copper(I)-based catalysts, such as Cu2S, are considered to be very promising materials for photocatalytic CO2 reduction. A common synthesis route for Cu2S via cation exchange from CdS nanocrystals requires Cu(I) precursors, organic solvents, and neutral atmosphere, but these conditions are not compatible with in situ applications in photocatalysis. Here we propose a novel cation exchange reaction that takes advantage of the reducing potential of photoexcited electrons in the conduction band of CdS and proceeds with Cu(II) precursors in an aqueous environment and under aerobic conditions. We show that the synthesized Cu2S photocatalyst can be efficiently used for the reduction of CO2 to carbon monoxide and methane, achieving formation rates of 3.02 and 0.13 μmol h(-1) g(-1), respectively, and suppressing competing water reduction. The process opens new pathways for the preparation of new efficient photocatalysts from readily available nanostructured templates. PMID:26479775

  5. Permeation and interaction of monovalent cations with the cGMP-gated channel of cone photoreceptors.

    PubMed

    Picones, A; Korenbrot, J I

    1992-10-01

    We measured the ion selectivity of cGMP-dependent currents in detached membrane patches from the outer segment of cone photoreceptors isolated from the retina of striped bass. In inside-out patches excised from either single or twin cones the amplitude of these currents, under symmetric ionic solutions, changed with the concentration of cGMP with a dependence described by a Hill equation with average values, at +80 mV, of Km = 42.6 microM and n = 2.49. In the absence of divalent cations, and under symmetric ionic solutions, the I-V curves of the currents were linear over the range of -80 to +80 mV. The addition of Ca altered the form of the I-V curve to a new function well described by an empirical equation that also describes the I-V curve of the photocurrent measured in intact photoreceptors. The monovalent cation permeability sequence of the cGMP-gated channels in the absence of divalent ions was PK > PNa = PLi = PRb > PCs (1.11 > 1.0 = 0.99 = 0.96 > 0.82). The conductance selectivity sequence at +80 mV was GNa = GK > GRb > GCs > GLi (1.0 = 0.99 > 0.88 > 0.74 > 0.60). The organic cations tetramethylammonium (TMA) and arginine partially blocked the current, but the larger ion, arginine, was permeant, whereas the smaller ion, TMA, was not. The amplitude of the outward current through the channels increased with the concentration of monovalent cations on the cytoplasmic membrane surface, up to a saturating value. The increase was well described by the adsorption isotherm of a single ion binding site within the channel with average binding constants, at +80 mV, of 104 mM for Na and 37.6 mM for Li. By assuming that the ion channel contains a single ion binding site in an energy trough separated from each membrane surface by an energy barrier, and using Eyring rate theory, we simulated I-V curves that fit the experimental data measured under ionic concentration gradients. From this fit we conclude that the binding site interacts with one ion at a time and that the

  6. Cationic influences upon synaptic transmission at the hair cell-afferent fiber synapse of the frog

    NASA Technical Reports Server (NTRS)

    Cochran, S. L.

    1995-01-01

    The concentrations of inorganic cations (K+, Na+, and Ca2+) bathing the isolated frog labyrinth were varied in order to assess their role in influencing and mediating synaptic transmission at the hair cell-afferent fiber synapse. Experiments employed intracellular recordings of synaptic activity from VIIIth nerve afferents. Recordings were digitized continuously at 50 kHz, and excitatory postsynaptic potentials were detected and parameters quantified by computer algorithms. Particular attention was focused on cationic effects upon excitatory postsynaptic potential frequency of occurrence and excitatory postsynaptic potential amplitude, in order to discriminate between pre- and postsynaptic actions. Because the small size of afferents preclude long term stable recordings, alterations in cationic concentrations were applied transiently and their peak effects on synaptic activity were assessed. Increases in extracellular K+ concentration of a few millimolar produced a large increase in the frequency of occurrence of excitatory postsynaptic potentials with little change in amplitude, indicating that release of transmitter from the hair cell is tightly coupled to its membrane potential. Increasing extracellular Na+ concentration resulted in an increase in excitatory postsynaptic potential amplitude with no significant change in excitatory postsynaptic potential frequency of occurrence, suggesting that the transmitter-gated subsynaptic channel conducts Na+ ions. Decreases in extracellular Ca2+ concentration had little effect upon excitatory postsynaptic potential frequency, but increased excitatory postsynaptic potential frequency and amplitude. These findings suggest that at higher concentrations Ca2+ act presynaptically to prevent transmitter release and postsynaptically to prevent Na+ influx during the generation of the excitatory postsynaptic potential. The influences of these ions on synaptic activity at this synapse are remarkably similar to those reported at the

  7. Alternating-current conductivity and dielectric relaxation of bulk iodoargentate

    SciTech Connect

    Duan, Hai-Bao Yu, Shan-Shan; Zhou, Hong

    2015-05-15

    Graphical abstract: The electric modulus shows single dielectric relaxation process in the measured frequency range. - Highlights: • The conduction mechanism is described by quantum mechanical tunneling model. • The applications of dielectric modulus give a simple method for evaluating the activation energy of the dielectric relaxation. • The [Ag{sub 2}I{sub 4}]{sup 2−}1-D chain and [Cu(en){sub 2}]{sup 2+} cation column form the layered stacks by hydrogen bond interactions. - Abstract: An inorganic-organic hybrid compound Cu(en){sub 2}Ag{sub 2}I{sub 4} (en = ethylenediamine) (1) was synthesized and single crystal structurally characterized. Along the [001] direction, the inorganic parts form an infinite 1-D chain and [Cu(en){sub 2}]{sup 2+} cations are separated by inorganic chain. The electrical conductivity and dielectric properties of 1 have been investigated over wide ranges of frequency. The alternating-current conductivities have been fitted to the Almond–West type power law expression with use of a single value of S. It is found that S values for 1 are nearly temperature-independent, which indicates that the conduction mechanism could be quantum mechanical tunneling (QMT) model. The dielectric loss and electric modulus show single dielectric relaxation process. The activation energy obtained from temperature-dependent electric modulus compare with the calculated from the dc conductivity plots.

  8. 21 CFR 872.3420 - Carboxymethylcellulose sodium and cationic polyacrylamide polymer denture adhesive.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... polyacrylamide polymer denture adhesive. 872.3420 Section 872.3420 Food and Drugs FOOD AND DRUG ADMINISTRATION....3420 Carboxymethylcellulose sodium and cationic polyacrylamide polymer denture adhesive. (a) Identification. A carboxymethylcellulose sodium and cationic polyacrylamide polymer denture adhesive is a...

  9. 21 CFR 872.3420 - Carboxymethylcellulose sodium and cationic polyacrylamide polymer denture adhesive.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... polyacrylamide polymer denture adhesive. 872.3420 Section 872.3420 Food and Drugs FOOD AND DRUG ADMINISTRATION....3420 Carboxymethylcellulose sodium and cationic polyacrylamide polymer denture adhesive. (a) Identification. A carboxymethylcellulose sodium and cationic polyacrylamide polymer denture adhesive is a...

  10. 21 CFR 872.3420 - Carboxymethylcellulose sodium and cationic polyacrylamide polymer denture adhesive.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... polyacrylamide polymer denture adhesive. 872.3420 Section 872.3420 Food and Drugs FOOD AND DRUG ADMINISTRATION....3420 Carboxymethylcellulose sodium and cationic polyacrylamide polymer denture adhesive. (a) Identification. A carboxymethylcellulose sodium and cationic polyacrylamide polymer denture adhesive is a...

  11. Preparing cationic cotton linter cellulose with high substitution degree by ultrasonic treatment.

    PubMed

    Zhang, Fulong; Pang, Zhiqiang; Dong, Cuihua; Liu, Zong

    2015-11-01

    As an important cellulose derivative, cationic cellulose has becoming an attractive material. However, it remains challenging to produce cationic cellulose with high substitute degree. In this paper, we successfully increased the substitute degree of cationic cellulose by introducing ultrasonic treatment, which efficiently breaks hydrogen bonds of the chemical structure of cationic cellulose. Properties of cationic cellulose were studied by scanning electron spectroscope (SEM), contact angle, X-ray diffraction (XRD) and thermogravimetric analysis (TGA). Experimental results show that the cationic cellulose has rougher surface and lower crystallinity degree as compared to the original sample. TGA analysis verifies that the thermostability of CLC decreases after the cationic modification. The residual of the cationic cellulose (25 wt%) after pyrolysis increases significantly as compared to that of the original cellulose (15 wt%). PMID:26256343

  12. Plant cation/H(+) exchangers (CAXs): biological functions and genetic manipulations

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Inorganic cations play decisive roles in many cellular and physiological processes and are essential components of plant nutrition. Therefore, the uptake of cations and their redistribution must be precisely controlled. Vacuolar antiporters are important elements in mediating the intracellular seque...

  13. Nanocarbonic transparent conductive films.

    PubMed

    Roth, Siegmar; Park, Hye Jin

    2010-07-01

    This tutorial review discusses the contradictory material properties of electrical conductivity and optical transparency for the examples of graphene films and carbon nanotube networks. It is argued that for homogeneous films both properties are linked by basic laws of physics and that for perfect monoatomic layers conductivity and transparency can be calculated from the fine structure constant. To beat these limitations, inhomogeneous films are required, such as graphene with an array of holes or nanotube networks. An overview is given on literature values of transparency and conductivity, both for graphene films and for nanotube networks. PMID:20502813

  14. Carbon as a Shallow Donor in Transparent Conducting Oxides

    NASA Astrophysics Data System (ADS)

    Lyons, J. L.; Steiauf, D.; Janotti, A.; Van de Walle, C. G.

    2014-12-01

    Carbon is a common unintentional impurity in oxide semiconductors. We use hybrid density functional theory to calculate the electronic and structural properties of carbon impurities in ZnO, In2O3 , and Ga2O3 —materials that are used as transparent conductors. In each of these semiconducting oxides, we find that carbon is most likely to occupy the cation site under most electronic and chemical potential conditions. In ZnO, CZn acts as a shallow double donor and exhibits large local breathing-mode relaxations. In In2O3 and Ga2O3 , C acts as a shallow donor and moves off the cation site to become threefold oxygen coordinated. In all three oxides, Ccation exhibits modest formation energies, indicating that these species will be likely to incorporate. Our results indicate that C impurities are suitable donor dopants in these oxides and will contribute to background n -type conductivity if unintentionally present.

  15. Multi-State Vibronic Interactions in Fluorinated Benzene Radical Cations.

    NASA Astrophysics Data System (ADS)

    Faraji, S.; Köppel, H.

    2009-06-01

    Conical intersections of potential energy surfaces have emerged as paradigms for signalling strong nonadiabatic coupling effects. An important class of systems where some of these effects have been analyzed in the literature, are the benzene and benzenoid cations, where the electronic structure, spectroscopy, and dynamics have received great attention in the literature. In the present work a brief overview is given over our theoretical treatments of multi-mode and multi-state vibronic interactions in the benzene radical cation and some of its fluorinated derivatives. The fluorobenzene derivatives are of systematic interest for at least two different reasons. (1) The reduction of symmetry by incomplete fluorination leads to a disappearance of the Jahn-Teller effect present in the parent cation. (2) A specific, more chemical effect of fluorination consists in the energetic increase of the lowest σ-type electronic states of the radical cations. The multi-mode multi-state vibronic interactions between the five lowest electronic states of the fluorobenzene radical cations are investigated theoretically, based on ab initio electronic structure data, and employing the well-established linear vibronic coupling model, augmented by quadratic coupling terms for the totally symmetric vibrational modes. Low-energy conical intersections, and strong vibronic couplings are found to prevail within the set of tilde{X}-tilde{A} and tilde{B}-tilde{C}-tilde{D} cationic states, while the interactions between these two sets of states are found to be weaker and depend on the particular isomer. This is attributed to the different location of the minima of the various conical intersections occurring in these systems. Wave-packet dynamical simulations for these coupled potential energy surfaces, utilizing the powerful multi-configuration time-dependent Hartree method are performed. Ultrafast internal conversion processes and the analysis of the MATI and photo-electron spectra shed new light

  16. Star-like superalkali cations featuring planar pentacoordinate carbon

    NASA Astrophysics Data System (ADS)

    Guo, Jin-Chang; Tian, Wen-Juan; Wang, Ying-Jin; Zhao, Xue-Feng; Wu, Yan-Bo; Zhai, Hua-Jin; Li, Si-Dian

    2016-06-01

    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 CBe5 can be modified to form a series of star-like superalkali ppC or quasi-ppC CBe5X5+ (X = F, Cl, Br, Li, Na, K) cations containing a CBe5 moiety. Polyhalogenation and polyalkalination on the CBe5 unit may help eliminate the high reactivity of bare CBe5 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 CBe5X5+ (X = F, Cl, Br, Li, Na, K) clusters are the true global minima of the systems. The predicted VEAs for CBe5X5+ 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 CBe5 motif is robust in the clusters. As planar hypercoordination carbon species are often thermodynamically unstable and

  17. Star-like superalkali cations featuring planar pentacoordinate carbon.

    PubMed

    Guo, Jin-Chang; Tian, Wen-Juan; Wang, Ying-Jin; Zhao, Xue-Feng; Wu, Yan-Bo; Zhai, Hua-Jin; Li, Si-Dian

    2016-06-28

    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 CBe5 can be modified to form a series of star-like superalkali ppC or quasi-ppC CBe5X5 (+) (X = F, Cl, Br, Li, Na, K) cations containing a CBe5 moiety. Polyhalogenation and polyalkalination on the CBe5 unit may help eliminate the high reactivity of bare CBe5 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 CBe5X5 (+) (X = F, Cl, Br, Li, Na, K) clusters are the true global minima of the systems. The predicted VEAs for CBe5X5 (+) 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 CBe5 motif is robust in the clusters. As planar hypercoordination carbon species are often thermodynamically

  18. Conductive polypyrrole/viscose fiber composites.

    PubMed

    Wang, Ning; Li, Guodong; Yu, Zhuo; Zhang, Xingxiang; Qi, Xiaoling

    2015-08-20

    Polypyrrole (PPy) was polymerized with pyrrole (Py) as the monomer, FeCl3 as an oxidant and sodium dodecyl benzene sulfonate (SDBS) as the dopant on the surface of viscose fiber (VCF) to prepare the conductive PPy/VCF composites. Fourier transform infrared spectra (FT-IR), thermal gravimetric analysis (TGA) and X-ray photoelectron spectroscope (XPS) proved that the interaction between PPy and VCF formed in the PPy/VCF composites. Three structures of N atoms (imine, amine and cationic atoms) were found in PPy of PPy/VCF composites. The influence of reaction conditions including reaction time, Py concentration, FeCl3 concentration and SDBS concentration on the morphology and the conductivity of PPy/VCF composites was investigated in detail. The orthogonal experiments were designed to determine the optimal reaction conditions: reaction time 5h, Py concentration 0.1 mol/L and FeCl3 concentration 0.25 mol/L. When PPy/VCF composite was washed 50 times in water, the conductivity still kept at 1.5S/cm, and this value was stable for more washing. PMID:25965491

  19. Contactless conductivity detector for microchip capillary electrophoresis

    NASA Technical Reports Server (NTRS)

    Pumera, Martin; Wang, Joseph; Opekar, Frantisek; Jelinek, Ivan; Feldman, Jason; Lowe, Holger; Hardt, Steffen; Svehla, D. (Principal Investigator)

    2002-01-01

    A microfabricated electrophoresis chip with an integrated contactless conductivity detection system is described. The new contactless conductivity microchip detector is based on placing two planar sensing aluminum film electrodes on the outer side of a poly(methyl methacrylate) (PMMA) microchip (without contacting the solution) and measuring the impedance of the solution in the separation channel. The contactless route obviates problems (e.g., fouling, unwanted reactions) associated with the electrode-solution contact, offers isolation of the detection system from high separation fields, does not compromise the separation efficiency, and greatly simplifies the detector fabrication. Relevant experimental variables, such as the frequency and amplitude of the applied ac voltage or the separation voltage, were examined and optimized. The detector performance was illustrated by the separation of potassium, sodium, barium, and lithium cations and the chloride, sulfate, fluoride, acetate, and phosphate anions. The response was linear (over the 20 microM-7 mM range) and reproducible (RSD = 3.4-4.9%; n = 10), with detection limits of 2.8 and 6.4 microM (for potassium and chloride, respectively). The advantages associated with the contactless conductivity detection, along with the low cost of the integrated PMMA chip/detection system, should enhance the power and scope of microfluidic analytical devices.

  20. Ionic conductivity and thermoelectric power of pure and Al2O3-dispersed AgI

    NASA Technical Reports Server (NTRS)

    Shahi, K.; Wagner, J. B., Jr.

    1981-01-01

    Ionic and electronic conductivities, and thermoelectric power have been measured for AgI and AgI containing a dispersion of submicron size Al2O3 particles. While the dispersion of Al2O3 enhances the ionic conductivity significantly, it does not affect the electronic properties of the matrix. The enhancement is a strong function of the size and concentration of the dispersoid. Various models have been tested to account for the enhanced conduction. However, the complex behavior of the present results points out the need for more sophisticated theoretical models. Ionic conduction and thermoelectric power data suggest that the dispersed Al2O3 generates an excess of cation vacancies and thereby enhances the conductivity and suppresses the thermoelectric power of the matrix. The individual heats of transport of cation interstitials and vacancies have been estimated and compared to their respective migration energies.

  1. Complex conductivity of organic-rich shales

    NASA Astrophysics Data System (ADS)

    Woodruff, W. F.; Revil, A.; Torres-Verdin, C.

    2013-12-01

    We can accurately determine the intrinsic anisotropy and material properties in the laboratory, providing empirical evidence of transverse isotropy and the polarization of the organic and metallic fractions in saturated and unsaturated shales. We develop two distinct approaches to obtain the complex conductivity tensor from spectral induced polarization (SIP) measurements. Experimental results indicate clear anisotropy, and characterize the effects of thermal maturation, TOC, and pyrite, aiding in the calibration and interpretation of geophysical data. SIP is a non-intrusive measurement, sensitive to the surface conductance of mineral grains, frequency-dependent polarization of the electrical double layer, and bulk conductivity of the pore water. The in-phase and quadrature components depend upon parameters of principal importance in unconventional shale formation evaluation (e.g., the distribution of pore throat sizes, formation factor, permeability, salinity and cation exchange capacity (CEC), fluid saturation and wettability). In addition to the contribution of the electrical double layer of non-conducting minerals to surface conductivity, we have observed a clear relaxation associated with kerogen pyrolysis, pyrite distribution, and evidence that the CEC of the kerogen fraction may also contribute, depending on thermal maturation history. We utilize a recent model for anisotropic complex conductivity, and rigorous experimental protocols to quantify the role of kerogen and pyrolysis on surface and quadrature conductivity in mudrocks. The complex conductivity tensor σ* describes the directional dependence of electrical conduction in a porous medium, and accounts for both conduction and polarization. The complex-valued tensor components are given as σ*ij , where σ'ij represents in-phase and σ"ij denotes quadrature conductivities. The directional dependence of the complex conductivity tensor is relegated to the textural properties of the material. The

  2. Cardiac conduction system

    MedlinePlus Videos and Cool Tools

    ... signals to the heart muscle causing it to contract. The main components of the cardiac conduction system ... the sequence by causing the atrial muscles to contract. From there, the signal travels to the AV ...

  3. Conductive open frameworks

    DOEpatents

    Yaghi, Omar M.; Wan, Shun; Doonan, Christian J.; Wang, Bo; Deng, Hexiang

    2016-02-23

    The disclosure relates generally to materials that comprise conductive covalent organic frameworks. The disclosure also relates to materials that are useful to store and separate gas molecules and sensors.

  4. Electrically conductive material

    DOEpatents

    Singh, J.P.; Bosak, A.L.; McPheeters, C.C.; Dees, D.W.

    1993-09-07

    An electrically conductive material is described for use in solid oxide fuel cells, electrochemical sensors for combustion exhaust, and various other applications possesses increased fracture toughness over available materials, while affording the same electrical conductivity. One embodiment of the sintered electrically conductive material consists essentially of cubic ZrO[sub 2] as a matrix and 6-19 wt. % monoclinic ZrO[sub 2] formed from particles having an average size equal to or greater than about 0.23 microns. Another embodiment of the electrically conductive material consists essentially at cubic ZrO[sub 2] as a matrix and 10-30 wt. % partially stabilized zirconia (PSZ) formed from particles having an average size of approximately 3 microns. 8 figures.

  5. Cardiac conduction system

    MedlinePlus Videos and Cool Tools

    ... cardiac muscle cells in the walls of the heart that send signals to the heart muscle causing it to contract. The main components ... the cardiac conduction system’s electrical activity in the heart.

  6. Solution Conductivity Apparatus.

    ERIC Educational Resources Information Center

    Haworth, Daniel T.; Bartelt, Mark R.; Kenney, Michael J.

    1999-01-01

    Describes the construction of a conductivity meter that includes a timer and a readout display that provides semiquantitative information. The meter can be made into a hand-held or lecture hall (demonstration) version. (WRM)

  7. Electrically conductive material

    DOEpatents

    Singh, Jitendra P.; Bosak, Andrea L.; McPheeters, Charles C.; Dees, Dennis W.

    1993-01-01

    An electrically conductive material for use in solid oxide fuel cells, electrochemical sensors for combustion exhaust, and various other applications possesses increased fracture toughness over available materials, while affording the same electrical conductivity. One embodiment of the sintered electrically conductive material consists essentially of cubic ZrO.sub.2 as a matrix and 6-19 wt. % monoclinic ZrO.sub.2 formed from particles having an average size equal to or greater than about 0.23 microns. Another embodiment of the electrically conductive material consists essentially at cubic ZrO.sub.2 as a matrix and 10-30 wt. % partially stabilized zirconia (PSZ) formed from particles having an average size of approximately 3 microns.

  8. 21 CFR 872.3480 - Polyacrylamide polymer (modified cationic) denture adhesive.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... adhesive. 872.3480 Section 872.3480 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND... polymer (modified cationic) denture adhesive. (a) Identification. A polyacrylamide polymer (modified cationic) denture adhesive is a device composed of polyacrylamide polymer (modified cationic) intended...

  9. 21 CFR 872.3480 - Polyacrylamide polymer (modified cationic) denture adhesive.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... adhesive. 872.3480 Section 872.3480 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND... polymer (modified cationic) denture adhesive. (a) Identification. A polyacrylamide polymer (modified cationic) denture adhesive is a device composed of polyacrylamide polymer (modified cationic) intended...

  10. 21 CFR 872.3480 - Polyacrylamide polymer (modified cationic) denture adhesive.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... adhesive. 872.3480 Section 872.3480 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND... polymer (modified cationic) denture adhesive. (a) Identification. A polyacrylamide polymer (modified cationic) denture adhesive is a device composed of polyacrylamide polymer (modified cationic) intended...

  11. ESR of the cation radicals from γ-irradiated ketenes in haloalkane and SF 6 matrices

    NASA Astrophysics Data System (ADS)

    Shimokoshi, Kazuo; Fujisawa, Jun; Nakamura, Kazutaka; Sato, Shin; Shida, Tadamasa

    1983-08-01

    The cation radicals of ketene and its methyl and ethyl derivatives have been produced in γ-irradiated solid solutions of haloalkanes and SF 6. From the observed isotropic proton hyperfine parameters of these cation radicals and UHF MO (INDO) calculations, the cations are found to be characteristic of ordinary π-radicals.

  12. Identification of three distinct phylogenetic groups of CAX Cation/Proton Antiporters

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Ca[2+]/cation antiporter (CaCA) proteins are integral membrane proteins that transport Ca[2+] or other cations using the H[+] or Na[+] gradient generated by primary transporters. The CAX (for CAtion eXchanger) family is one of the five families that make up the CaCA superfamily. CAX genes have been ...

  13. Two cationic peroxidases from cell walls of Araucaria araucana seeds.

    PubMed

    Riquelme, A; Cardemil, L

    1995-05-01

    We have previously reported the purification and partial characterization of two cationic peroxidases from the cell walls of seeds and seedlings of the South American conifer, Araucaria araucana. In this work, we have studied the amino acid composition and NH2-terminal sequences of both enzymes. We also compare the data obtained from these analyses with those reported for other plant peroxidases. The two peroxidases are similar in their amino acid compositions. Both are particularly rich in glycine, which comprises more than 30% of the amino acid residues. The content of serine is also high, ca 17%. The two enzymes are different in their content of arginine, alanine, valine, phenylalanine and threonine. Both peroxidases have identical NH2-terminal sequences, indicating that the two proteins are genetically related and probably are isoforms of the same kind of peroxidase. The amino acid composition and NH2-terminal sequence analyses showed marked differences from the cationic peroxidases from turnip and horseradish. PMID:7786490

  14. The perforin pore facilitates the delivery of cationic cargos.

    PubMed

    Stewart, Sarah E; Kondos, Stephanie C; Matthews, Antony Y; D'Angelo, Michael E; Dunstone, Michelle A; Whisstock, James C; Trapani, Joseph A; Bird, Phillip I

    2014-03-28

    Cytotoxic lymphocytes eliminate virally infected or neoplastic cells through the action of cytotoxic proteases (granzymes). The pore-forming protein perforin is essential for delivery of granzymes into the cytoplasm of target cells; however the mechanism of this delivery is incompletely understood. Perforin contains a membrane attack complex/perforin (MACPF) domain and oligomerizes to form an aqueous pore in the plasma membrane; therefore the simplest (and best supported) model suggests that granzymes passively diffuse through the perforin pore into the cytoplasm of the target cell. Here we demonstrate that perforin preferentially delivers cationic molecules while anionic and neutral cargoes are delivered inefficiently. Furthermore, another distantly related pore-forming MACPF protein, pleurotolysin (from the oyster mushroom), also favors the delivery of cationic molecules, and efficiently delivers human granzyme B. We propose that this facilitated diffusion is due to conserved features of oligomerized MACPF proteins, which may include an anionic lumen. PMID:24558045

  15. A Supramolecularly Activated Radical Cation for Accelerated Catalytic Oxidation.

    PubMed

    Jiao, Yang; Li, Wan-Lu; Xu, Jiang-Fei; Wang, Guangtong; Li, Jun; Wang, Zhiqiang; Zhang, Xi

    2016-07-25

    Tuning the activity of radicals is crucial for radical reactions and radical-based materials. Herein, we report a supramolecular strategy to accelerate the Fenton reaction through the construction of supramolecularly activated radical cations. As a proof of the concept, cucurbit[7]uril (CB[7]) was introduced, through host-guest interactions, onto each side of a derivative of 1,4-diketopyrrolo[3,4-c]pyrrole (DPP), a model dye for Fenton oxidation. The DPP radical cation, the key intermediate in the oxidation process, was activated by the electrostatically negative carbonyl groups of CB[7]. The activation induced a drastic decrease in the apparent activation energy and greatly increased the reaction rate. This facile supramolecular strategy is a promising method for promoting radical reactions. It may also open up a new route for the catalytic oxidation of organic pollutants for water purification and widen the realm of supramolecular catalysis. PMID:27273046

  16. Cationic Fullerenes Are Effective and Selective Antimicrobial Photosensitizers

    PubMed Central

    Tegos, George P.; Demidova, Tatiana N.; Arcila-Lopez, Dennisse; Lee, Haeryeon; Wharton, Tim; Gali, Hariprasad; Hamblin, Michael R.

    2011-01-01

    Summary Fullerenes are soccer ball-shaped molecules composed of carbon atoms, and, when derivatized with functional groups, they become soluble and can act as photosensitizers. Antimicrobial photodynamic therapy combines a nontoxic photosensitizer with harmless visible light to generate reactive oxygen species that kill microbial cells. We have compared the antimicrobial activity of six functionalized C60 compounds with one, two, or three hydrophilic or cationic groups in combination with white light against gram-positive bacteria, gram-negative bacteria, and fungi. After a 10 min incubation, the bis- and tris-cationic fullerenes were highly active in killing all tested microbes (4–6 logs) under conditions in which mammalian cells were comparatively unharmed. These compounds performed significantly better than a widely used antimicrobial photosensitizer, toluidine blue O. The high selectivity and efficacy exhibited by these photosensitizers encourage further testing for antimicrobial applications. PMID:16242655

  17. Carotenoid cation radicals: electrochemical, optical, and EPR study

    SciTech Connect

    Grant, J.L.; Kramer, V.J.; Ding, R.; Kispert, L.D.

    1988-03-30

    The general aim of this investigation is to determine whether carotenoid cation radicals can be produced, and stabilized, electrochemically. Hence, the authors have undertaken a detailed study of the electrooxidation of various carotenoids (..beta..-carotene (I), ..beta..-apo-8'-carotenal (II), and canthaxanthin (III) using the techniques of cyclic voltammetry, controlled-potential electrolysis (cpe) in conjunction with optical spectroscopy, and EPR spectroscopy coupled with in situ electrolysis. They report the successful generation of carotenoid cation radicals via electrochemical oxidation and, furthermore, the stabilization of these radicals for several minutes in CH/sub 2/Cl/sub 2/ and C/sub 2/H/sub 4/Cl/sub 2/ solvents.

  18. Cationic porphycenes as potential photosensitizers for antimicrobial photodynamic therapy

    PubMed Central

    Ragàs, Xavier; Sánchez-García, David; Ruiz-González, Rubén; Dai, Tianhong; Agut, Montserrat; Hamblin, Michael R.; Nonell, Santi

    2010-01-01

    Structures of typical photosensitizers used in antimicrobial photodynamic therapy are based on porphyrins, phthalocyanines and phenothiazinium salts, with cationic charges at physiological pH values. However derivatives of the porphycene macrocycle (a structural isomer of porphyrin) have barely been investigated as antimicrobial agents. Therefore, we report the synthesis of the first tricationic water-soluble porphycene and its basic photochemical properties. We successfully tested it for in vitro photoinactivation of different Gram-positive and Gram-negative bacteria, as well as a fungal species (Candida) in a drug-dose and light-dose dependent manner. We also used the cationic porphycene in vivo to treat an infection model comprising mouse 3rd degree burns infected with a bioluminescent methicillin-resistant Staphylococcus aureus strain. There was a 2.6-log10 reduction (p < 0.001) of the bacterial bioluminescence for the PDT-treated group after irradiation with 180 J·cm-2 of red light. PMID:20936792

  19. Removal of both cationic and anionic contaminants by amphoteric starch.

    PubMed

    Peng, Huanlong; Zhong, Songxiong; Lin, Qintie; Yao, Xiaosheng; Liang, Zhuoying; Yang, Muqun; Yin, Guangcai; Liu, Qianjun; He, Hongfei

    2016-03-15

    A novel amphoteric starch incorporating quaternary ammonium and phosphate groups was applied to investigate the efficiency and mechanism of cationic and anionic contaminant treatment. Its flocculation abilities for kaolin suspension and copper-containing wastewater were evaluated by turbidity reduction and copper removal efficiency, respectively. And the kinetics of formation, breakage and subsequent re-formation of aggregates were monitored using a Photometric Dispersion Analyzer (PDA) and characterized by flocculation index (FI). The results showed that amphoteric starch possessed the advantages of being lower-dosages-consuming and being stronger in shear resistance than cationic starch, and exhibited a good flocculation efficiency over a wide pH range from 3.0 to 11.0. PMID:26794754

  20. Polyoxometalate salts of cationic nitronyl nitroxide free radicals

    NASA Astrophysics Data System (ADS)

    Coronado, Eugenio; Giménez-Saiz, Carlos; Gómez-García, Carlos J.; Romero, Francisco M.

    2008-12-01

    The cationic nitronyl nitroxide free radical of the N-methylpyridinium type p-MepyNN + has been combined with [Mo 8O 26] 4- and Keggin [SiW 12O 40] 4- polyanions to afford salts ( p-MepyNN) 4[Mo 8O 26]·DMSO (DMSO = dimethylsulfoxide) ( 1) and ( p-MepyNN) 4[SiW 12O 40]·6DMF (DMF = dimethylformamide) ( 2). Herein, their structural and magnetic properties are described.

  1. Intramolecular interaction and dynamics of the cationic argon trimer

    SciTech Connect

    Ragnetti, F.; Zuhrt, C.; Zuelicke, L.

    1996-12-31

    For the simplest cationic argon cluster, Ar{sub 3}{sup +}, the topographical characteristics of the ground-state potential energy surface (PES), the mode coupling and the claswsical intramolecular dynamics are studied; PES data have been obtained by the diatomics-in-molecules approach of Kuntz et al. The results show that Ar{sub 3}{sup +} s a rather floppy system with rapid vibrational energy redistribution and early onset of classical chaos.

  2. Cation channels, cell volume and the death of an erythrocyte.

    PubMed

    Lang, Florian; Lang, Karl S; Wieder, Thomas; Myssina, Svetlana; Birka, Christina; Lang, Philipp A; Kaiser, Stephanie; Kempe, Daniela; Duranton, Christophe; Huber, Stephan M

    2003-11-01

    Similar to a variety of nucleated cells, human erythrocytes activate a non-selective cation channel upon osmotic cell shrinkage. Further stimuli of channel activation include oxidative stress, energy depletion and extracellular removal of Cl-. The channel is permeable to Ca2+ and opening of the channel increases cytosolic [Ca2+]. Intriguing evidence points to a role of this channel in the elimination of erythrocytes by apoptosis. Ca2+ entering through the cation channel stimulates a scramblase, leading to breakdown of cell membrane phosphatidylserine asymmetry, and stimulates Ca(2+)-sensitive K+ channels, thus leading to KCl loss and (further) cell shrinkage. The breakdown of phosphatidylserine asymmetry is evidenced by annexin binding, a typical feature of apoptotic cells. The effects of osmotic shock, oxidative stress and energy depletion on annexin binding are mimicked by the Ca2+ ionophore ionomycin (1 microM) and blunted in the nominal absence of extracellular Ca2+. Nevertheless, the residual annexin binding points to additional mechanisms involved in the triggering of the scramblase. The exposure of phosphatidylserine at the extracellular face of the cell membrane stimulates phagocytes to engulf the apoptotic erythrocytes. Thus, sustained activation of the cation channels eventually leads to clearance of affected erythrocytes from peripheral blood. Susceptibility to annexin binding is enhanced in several genetic disorders affecting erythrocyte function, such as thalassaemia, sickle-cell disease and glucose-6-phosphate dehydrogenase deficiency. The enhanced vulnerability presumably contributes to the shortened life span of the affected erythrocytes. Beyond their role in the limitation of erythrocyte survival, cation channels may contribute to the triggering of apoptosis in nucleated cells exposed to osmotic shock and/or oxidative stress. PMID:12905029

  3. Cation binding of antimicrobial sulfathiazole to leonardite humic acid.

    PubMed

    Richter, Merle K; Sander, Michael; Krauss, Martin; Christl, Iso; Dahinden, Manuel G; Schneider, Manuel K; Schwarzenbach, René P

    2009-09-01

    Sorption of sulfathiazole (STA) and three structural analogs to Leonardite humic acid (LHA) was investigated in single- and binary-solute systems to elucidate the sorption mechanism of sulfonamides to soil organic matter (SOM). Cation binding of STA+ to anionic sites A- in LHA governed sorption up to circumneutral pH, based on the following findings: (i) From pH 7.7 to 3.3, the increase in extent and nonlinearity (i.e., concentration dependence) of STA sorption paralleled the increase in STA+. (ii) From pH 3.3 to 1.7, sorption decreased and nonlinearity increased, consistent with strong competition of STA+ and H+ for A-. (iii) Replacement of the protonable aniline group in STA by an apolar methylbenzene group resulted in much weaker, linear, and pH-independent sorption. (iv) Only analogs with aniline moieties displaced STA from LHA in binary-solute systems. Displacement occurred up to pH 5.4, at which <1% of STA in solution was cationic. (v) STA sorption was well-described (R2 = 0.98) by the NICA-Donnan cation-binding model, yielding high median affinities for STA+ to carboxylic and phenolic A- (log K(STA+,1) = 3.25 +/- 0.08 log (L mol(-1)) and log K(STA+,2) = 8.76 +/- 0.11 log (L mol(-1)), respectively). High affinity cation binding explains sorption of polar sulfonamides in agricultural soils and the strong dependence of sorption on SOM content and pH. PMID:19764228

  4. Cationic PAMAM Dendrimers Aggressively Initiate Blood Clot Formation

    PubMed Central

    Jones, Clinton F.; Campbell, Robert A.; Brooks, Amanda E.; Assemi, Shoeleh; Tadjiki, Soheyl; Thiagarajan, Giridhar; Mulcock, Cheyanne; Weyrich, Andrew S.; Brooks, Benjamin D.; Ghandehari, Hamidreza; Grainger, David W.

    2012-01-01

    Poly(amidoamine) (PAMAM) dendrimers are increasingly studied as model nanoparticles for a variety of biomedical applications, notably in systemic administrations. However, with respect to blood contacting applications, amine-terminated dendrimers have recently been shown to activate platelets and cause a fatal, disseminated intravascular coagulation (DIC)-like condition in mice and rats. We here demonstrate that, upon addition to blood, cationic G7 PAMAM dendrimers induce fibrinogen aggregation, which may contribute to the in vivo DIC-like phenomenon. We demonstrate that amine-terminated dendrimers act directly on fibrinogen in a thrombin-independent manner to generate dense, high-molecular-weight fibrinogen aggregates with minimal fibrin fibril formation. In addition, we hypothesize this clot-like behavior is likely mediated through electrostatic interactions between the densely charged cationic dendrimer surface and negatively charged fibrinogen domains. Interestingly, cationic dendrimers also induced aggregation of albumin, suggesting that many negatively charged blood proteins may be affected by cationic dendrimers. To investigate this further, zebrafish embryos (ZFE) were employed to more specifically determine the speed of this phenomenon and the pathway- and dose-dependency of the resulting vascular occlusion phenotype. These novel findings show that G7 PAMAM dendrimers significantly and adversely impact many blood components to produce rapid coagulation and strongly suggest that these effects are independent of classic coagulation mechanisms. These results also strongly suggest the need to fully characterize amine-terminated PAMAM dendrimers in regards to their adverse effects on both coagulation and platelets, which may contribute to blood toxicity. PMID:23062017

  5. Electrophilic phosphonium cations catalyze hydroarylation and hydrothiolation of olefins.

    PubMed

    Pérez, Manuel; Mahdi, Tayseer; Hounjet, Lindsay J; Stephan, Douglas W

    2015-06-30

    Electrophilic phosphonium cations (EPCs) are efficient main group catalysts for the hydroarylation of olefins under mild conditions, providing a facile route to substituted aniline, bis-arylamine, phenol, furan, thiophene, pyrrole, and indole derivatives. Similarly, EPCs catalyze the hydrothiolation of aryl olefins with thiophenol affording a series of alkyl aryl thioethers. Experimental data support a mechanism for these reactions that involves initial activation of the olefin. PMID:26083901

  6. Proton conducting cerate ceramics

    SciTech Connect

    Coffey, G.W.; Pederson, L.R.; Armstrong, T.R.; Bates, J.L.; Weber, W.J.

    1995-08-01

    Cerate perovskites of the general formula AM{sub x}Ce{sub 1-x}O{sub 3-{delta}}, where A = Sr or Ba and where M = Gd, Nd, Y, Yb or other rare earth dopant, are known to conduct a protonic current. Such materials may be useful as the electrolyte in a solid oxide fuel cell operating at intermediate temperatures, as an electrochemical hydrogen separation membrane, or as a hydrogen sensor. Conduction mechanisms in these materials were evaluated using dc cyclic voltammetry and mass spectrometry, allowing currents and activation energies for proton, electron, and oxygen ion contributions to the total current to be determined. For SrYb{sub 0.05}Ce{sub 0.95}O{sub 3-{delta}}, one of the best and most environmentally stable compositions, proton conduction followed two different mechanisms: a low temperature process, characterized by an activation energy of 0.42{+-}0.04 eV, and a high temperature process, characterized by an activation energy of 1.38{+-}0.13 eV. It is believed that the low temperature process is dominated by grain boundary conduction while bulk conduction is responsible for the high temperature process. The activation energy for oxygen ion conduction (0.97{+-}0.10 eV) agrees well with other oxygen conductors, while that for electronic conduction, 0.90{+-}0.09 eV, is affected by a temperature-dependent electron carrier concentration. Evaluated by direct measurement of mass flux through a dense ceramic with an applied dc field, oxygen ions were determined to be the majority charge carrier except at the lowest temperatures, followed by electrons and then protons.

  7. Modulation of Group I Ribozyme Activity by Cationic Porphyrins

    PubMed Central

    Matsumura, Shigeyoshi; Ito, Tatsunobu; Tanaka, Takahiro; Furuta, Hiroyuki; Ikawa, Yoshiya

    2015-01-01

    The effects of cationic porphyrins on the catalytic activities of four group I ribozymes were investigated. A cationic porphyrin possessing four pyridinium moieties (pPyP) inhibited two group IC3 ribozymes (Syn Rz and Azo Rz) and a group IC1 ribozyme (Tet Rz). In the case of a group IA2 ribozyme (Td Rz), however, pPyP served not only as an inhibitor but also as an activator, and the effects of pPyP were dependent on its concentration. To analyze the structural and electronic factors determining the effects of pPyP on group I ribozymes, three cationic porphyrins (pPyNCP, pPyF4P, and TMPyP) were also examined. As interactions between small organic molecules and nucleic acids are attractive and important issues in biochemistry and biotechnology, this study contributes to the development of porphyrin-based molecules that can modulate functions of structured RNA molecules. PMID:25811638

  8. Structural Chemistry of Cation-Reacted Bacteriogenic UO2

    NASA Astrophysics Data System (ADS)

    Schofield, E.; Bargar, J.; Bernier-Latmani, R.; Sharp, J.; Veeramani, H.; Clark, D.; Conradson, S.; Mehta, A.

    2007-12-01

    The chemical stability of bacteriogenic uraninite, "UO2", is one of the seminal issues governing its success as an in-situ immobilization strategy in contaminated subsurface locations. Little detail is known about the structure and reactivity of this material, but based on comparison to its closest abiotic analog, UO2+x (0 < x < 0.25), we expect that it is complex and disordered, likely to exhibit non-stoichiometry, and capable of structurally incorporating common ground water cations and U(VI). Such fundamental changes in mineralogy are expected to substantially impact its stability in ground water. In this study, the product of microbial U(VI) reduction under varying conditions of pH, carbonate and divalent cation concentration was investigated. To facilitate x-ray scattering and oxidation kinetics measurements, cleaning methods were investigated to separate the biooxide and organic components. The local and long-range atomic and nano-scale structures of the wet oxides have been measured using EXAFS, WAXS, XPS and TEM. The lattice parameter of the nanoparticulate phase is seen to be consistent with bulk UO2. The first oxygen shell is distorted, indicating a nonstoichiometric composition. A significant change in the lattice parameter and local structure is produced when bacteriogenic UO2 is reacted with divalent cations and NaOH. These findings suggest that bacteriogenic UO2 and its reactivity can be modified by groundwater composition.

  9. Mono- and di-cationic hydrido boron compounds.

    PubMed

    Ghadwal, Rajendra S; Schürmann, Christian J; Andrada, Diego M; Frenking, Gernot

    2015-08-28

    Brønsted acid HNTf2 (Tf = SO2CF3) mediated dehydrogenative hydride abstraction from (L(1))BH3 () and (L(2))BH3 () (L(1) = IPrCH2 = 1,3-(2,6-di-isopropylphenyl)imidazol-2-methylidene (); L(2) = SIPrCH2 = 1,3-(2,6-di-isopropylphenyl)imidazolidin-2-methylidiene ()) affords thermally stable hydride bridged mono-cationic hydrido boron compounds [{(L(1))BH2}2(μ-H)](NTf2) () and [{(L(2))BH2}2(μ-H)](NTf2) (). Furthermore, hydride abstraction yields di-cationic hydrido boron compounds [{(L(1))BH}2(μ-H)2](NTf2)2 () and [{(L(2))BH}2(μ-H)2](NTf2)2 (). Unique cationic boron compounds with CH2BH2(μ-H)BH2CH2 ( and ) and CH2BH(μ-H)2BHCH2 ( and ) moieties feature a 3c-2e bond and have been fully characterized. Interesting electronic and structural features of compounds are analysed using spectroscopic, crystallographic, and computational methods. PMID:26200103

  10. Cationic porphyrin derivatives for application in photodynamic therapy of cancer

    NASA Astrophysics Data System (ADS)

    Prack McCormick, Bárbara P.; Florencia Pansa, M.; Milla Sanabria, Laura N.; Carvalho, Carla M. B.; Faustino, M. Amparo F.; Neves, Maria Graça P. M. S.; Cavaleiro, José A. S.; Rumie Vittar, Natalia B.; Rivarola, Viviana A.

    2014-04-01

    Current studies in photodynamic therapy (PDT) against cancer are focused on the development of new photosensitizers (PSs), with higher phototoxic action. The aim of this study was to compare the therapeutic efficiency of tri-cationic meso-substituted porphyrin derivatives (Tri-Py+-Me-PF, Tri-Py+-Me-Ph, Tri-Py+-Me-CO2Me and Tri-Py+-Me-CO2H) with the well-known tetra-cationic T4PM. The phototoxic action of these derivatives was assessed in human colon adenocarcinoma cells by cell viability, intracellular localization and nuclear morphology analysis. In the experimental conditions used we determined that after light activation -PF, -Ph and -CO2Me cause a more significant decline of cell viability compared to -CO2H and T4PM. These results suggest that the nature of the peripheral substituent influences the extent of cell photodamage. Moreover, we have demonstrated that PS concentration, physicochemical properties and further light activation determine the PDT response. All porphyrins were clearly localized as a punctuated pattern in the cytoplasm of the cells, and the PDT scheme resulted in apoptotic cell death after 3 h post-PDT. The tri-cationic porphyrin derivatives Tri-Py+-Me-PF, Tri-Py+-Me-Ph and Tri-Py+-Me-CO2Me showed a promising ability, making them good photosensitizer candidates for oncological PDT.

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

    SciTech Connect

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

    2008-12-18

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

  12. Cationic polymer mud solves gumbo problems in North Sea

    SciTech Connect

    Welch, O.; Lee, L.J. )

    1992-07-13

    This paper reports on a recently developed cationic polymer mud, compatible with conventional polymer additives and designed to meet environmental regulations, which significantly minimized the gumbo problems common to the water-sensitive shales in the North Sea. The cationic polymer mud was used to drill highly reactive Tertiary shale formations which have caused severe gumbo problems on nearby wells drilled with other inhibitive water-based muds. Although many citonic polymers are toxic, aquatic toxicity tests performed by the Norwegian Statens Forurensningstilsyn (SFT) at the end of the test wells showed results far exceeding the SFT limits on the three species tested. The mud system on these wells was a seawater-based 15.0-ppg mud enhanced with 3% NaCl. A low molecular weight quaternary polyamine and a high molecular weight cationic polyacrylamide were used to suppress the swelling and dispersion of shales, respectively. Starch and polyanionic cellulose (PAC) polymers maintained fluid-loss control, and a lubricant reduced the torque and drag.

  13. Electron beam curing of epoxy resins by cationic polymerization

    SciTech Connect

    Janke, C.J.; Dorsey, G.F.; Havens, S.J.; Lopata, V.J.

    1995-10-01

    Preliminary investigations have determined that conventional epoxy resins can be cured at selectable temperatures with high glass transition temperatures (essentially the same as with thermal curing), while still exhibiting equivalent or comparable mechanical properties. A cationic photoinitiator at a concentration of 1--3 parts per hundred of the epoxy resin is required for this process. Gamma cell screening of cationic photoinitiators with bisphenol A, bisphenol F, and cycloaliphatic epoxies demonstrated that diaryliodonium salts of weakly nucleophilic anions such as hexafluoroantimonate are most effective. Diaryliodonium salts were also found to be most effective initiators for the cationic polymerization of epoxy resins when a high energy/power electron beam accelerator was used as the source of ionizing radiation. For example Dow Tactix 123 (bisphenol A epoxy) containing 3 phr (4-octyloxyphenyl)phenyliodonium hexafluoroantimonate was irradiated at a total dosage of 100 kGy. Glass transition temperature (tan delta) of the cured material as determined by dynamic mechanical analysis was 182 C as compared to 165 C thermally cured material.

  14. Oxygen and cation diffusion in YBCO coated conductors

    NASA Astrophysics Data System (ADS)

    Tsukui, S.; Koritala, R. E.; Li, M.; Goretta, K. C.; Adachi, M.; Baker, J. E.; Routbort, J. L.

    2003-10-01

    Biaxially textured YBa 2Cu 3O x (YBCO) films 0.3 μm thick were deposited on single-crystal LaAlO 3 and buffered Hastelloy C276 substrates. After annealing in 18O at 400 °C, secondary-ion mass spectrometry was used to determine oxygen-diffusion profiles and several cation-diffusion profiles within the various layers of the conductors. Oxygenation in the YBCO/LaAlO 3 specimen was relatively slow and hours would be required for full oxygenation of the YBCO. Oxygen diffusion was rapid in the coated conductor. It was dominated by diffusion along a- b planes and full oxygenation of a 0.3-μm-thick YBCO layer was achieved in several minutes. Cation interdiffusion was limited in the YBCO/LaAlO 3 specimen, but was significant within the coated conductor. Although Cu diffused out of the superconductor, an SrTiO 3 layer between textured MgO and YBCO limited diffusion of cations from the various substrate layers into the superconductor.

  15. Specific cationic emission of cisplatin following ionization by swift protons

    NASA Astrophysics Data System (ADS)

    Moretto-Capelle, Patrick; Champeaux, Jean-Philippe; Deville, Charlotte; Sence, Martine; Cafarelli, Pierre

    2016-05-01

    We have investigated collision-induced ionization and fragmentation by 100 keV protons of the radio sensitizing molecule cisplatin, which is used in cancer treatments. A large emission of HCl+ and NH2+ is observed, but surprisingly, no cationic fragments containing platinum are detected, in contrast to ionization-dissociation induced by electronic collision. Theoretical investigations show that the ionization processes take place on platinum and on chlorine atoms. We propose new ionization potentials for cisplatin. Dissociation limits corresponding to the measured fragmentation mass spectrum have been evaluated and the theoretical results show that the non-observed cationic fragments containing platinum are mostly associated with low dissociation energies. We have also investigated the reaction path for the hydrogen transfer from the NH3 group to the Cl atom, as well as the corresponding dissociation limits from this tautomeric form. Here again the cations containing platinum correspond to lower dissociation limits. Thus, the experimental results suggest that excited states, probably formed via inner-shell ionization of the platinum atom of the molecule, correlated to higher dissociation limits are favored.

  16. Chromatographic behaviors of proteins on cation-exchange column.

    PubMed

    Li, Rong; Chen, Guo-Liang; Zhao, Wen-Ming

    2004-12-01

    A weak cation-exchanger (XIDACE-WCX) has been synthesized by the indirect method. The chromatographic characteristics of the synthesized packing was studied in detail. The standard protein mixture and lysozyme from egg white were separated with the prepared chromatographic column. The chromatographic thermodynamics of proteins was studied in a wide temperature range. Thermodynamic parameters standard enthalpy change (deltaH0) and standard entropy change (deltaS0) and compensation temperature (beta) at protein denaturation were determined in the chromatographic system. By using obtained deltaS0, the conformational change of proteins was judged in the chromatographic process. The linear relationship between deltaH0 and deltaS0 can be used to identify the identity of the protein retention mechanism in the weak cation-exchange chromatography. The interaction between weak cation-exchanger and metal ions was investigated. Several metal chelate columns were prepared. The effects of introducing metal ion into the naked column on protein retention and the retention mechanism of proteins in the metal chalet affinity chromatography were discussed. PMID:15689030

  17. Association between cationic liposomes and low molecular weight hyaluronic acid.

    PubMed

    Gasperini, Antonio A M; Puentes-Martinez, Ximena E; Balbino, Tiago Albertini; Rigoletto, Thais de Paula; Corrêa, Gabriela de Sá Cavalcanti; Cassago, Alexandre; Portugal, Rodrigo Villares; de La Torre, Lucimara Gaziola; Cavalcanti, Leide P

    2015-03-24

    This work presents a study of the association between low molecular weight hyaluronic acid (16 kDa HA) and cationic liposomes composed of egg phosphatidylcholine (EPC), 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE), and 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP). The cationic liposome/HA complexes were evaluated to determine their mesoscopic structure, average size, zeta potential, and morphology as a function of the amount of HA in the system. Small angle X-ray scattering results revealed that neighboring cationic liposomes either stick together after a partial coating of low concentration HA or disperse completely in excess of HA, but they never assemble as multilamellar vesicles. Cryo-transmission electron microscopy images confirm the existence of unilamellar vesicles and large aggregates of unilamellar vesicles for HA fractions up to 80% (w/w). High concentrations of HA (> 20% w/w) proved to be efficient for coating extruded liposomes, leading to particle complexes with sizes in the nanoscale range and a negative zeta potential. PMID:25730494

  18. Nucleophilic Addition of Nitrogen to Aryl Cations: Mimicking Titan Chemistry

    NASA Astrophysics Data System (ADS)

    Li, Anyin; Jjunju, Fred P. M.; Cooks, R. Graham

    2013-11-01

    The reactivity of aryl cations toward molecular nitrogen is studied systematically in an ion trap mass spectrometer at 102 Pascal of nitrogen, the pressure of the Titan main haze layer. Nucleophilic addition of dinitrogen occurs and the nature of aryl group has a significant influence on the reactivity, through inductive effects and by changing the ground state spin multiplicity. The products of nitrogen activation, aryldiazonium ions, react with typical nitriles, aromatic amines, and alkynes (compounds that are relevant as possible Titan atmosphere constituents) to form covalently bonded heterocyclic products. Theoretical calculations at the level [DFT(B3LYP)/6-311++G(d,p)] indicate that the N2 addition reaction is exothermic for the singlet aryl cations but endothermic for their triplet spin isomers. The -OH and -NH2 substituted aryl ions are calculated to have triplet ground states, which is consistent with their decreased nitrogen addition reactivity. The energy needed for the generation of the aryl cations from their protonated precursors (ca. 340 kJ/mol starting with protonated aniline) is far less than that required to directly activate the nitrogen triple bond (the lowest energy excited state of N2 lies ca. 600 kJ/mol above the ground state). The formation of aza-aromatics via arene ionization and subsequent reactions provide a conceivable route to the genesis of nitrogen-containing organic molecules in the interstellar medium and Titan haze layers.

  19. Cation-size-mismatch tuning of photoluminescence in oxynitride phosphors.

    PubMed

    Chen, Wei-Ting; Sheu, Hwo-Shuenn; Liu, Ru-Shi; Attfield, J Paul

    2012-05-16

    Red or yellow phosphors excited by a blue light-emitting diode are an efficient source of white light for everyday applications. Many solid oxides and nitrides, particularly silicon nitride-based materials such as M(2)Si(5)N(8) and MSi(2)O(2)N(2) (M = Ca, Sr, Ba), CaAlSiN(3), and SiAlON, are useful phosphor hosts with good thermal stabilities. Both oxide/nitride and various cation substitutions are commonly used to shift the emission spectrum and optimize luminescent properties, but the underlying mechanisms are not always clear. Here we show that size-mismatch between host and dopant cations tunes photoluminescence shifts systematically in M(1.95)Eu(0.05)Si(5-x)Al(x)N(8-x)O(x) lattices, leading to a red shift when the M = Ba and Sr host cations are larger than the Eu(2+) dopant, but a blue shift when the M = Ca host is smaller. Size-mismatch tuning of thermal quenching is also observed. A local anion clustering mechanism in which Eu(2+) gains excess nitride coordination in the M = Ba and Sr structures, but excess oxide in the Ca analogues, is proposed for these mismatch effects. This mechanism is predicted to be general to oxynitride materials and will be useful in tuning optical and other properties that are sensitive to local coordination environments. PMID:22534019

  20. Role of cation choice in the radiation tolerance of pyrochlores

    SciTech Connect

    Devanathan, Ramaswami; Gao, Fei; Sundgren, Christina J.

    2012-12-21

    We have used atomistic computer simulations to study anion diffusion coefficients and the response to swift heavy ion irradiation of Gd2TixZr2-xO7 pyrochlore for x values of 0, 0.5, 1, 1.5 and 2. In Gd2Ti2O7, thermal energy deposition per unit length of 12 keV/nm results in a cylindrical amorphous track of radius 2 nm in good agreement with experiment. The volume swelling of the track is 4%, which suggests that it is partially amorphous. Gd vacancies and Ti interstitials along with cation exchange play a role in damage accumulation in the titanate. In sharp contrast, Gd2Zr2O7 does not swell and merely transforms from fluorite to pyrochlore under the same conditions. The activation energy barrier for oxygen hopping by the vacancy mechanism in these pyrochlores is 0.26-0.44 eV. The radiation tolerance of gadolinium zirconate pyrochlore is related to the efficient annihilation of cation Frenkel pairs, the low energy cost and negligible volume expansion associated with the resulting cation exchange, and efficient annealing of anion sublattice damage.

  1. Determination of the cation-exchange capacity of muscovite mica

    SciTech Connect

    Osman, M.A.; Suter, U.W.

    2000-04-01

    High cation-exchange capacity (CEC) muscovite mica with a homoionic surface was prepared by replacing the Li{sup +} surface ions of partially delaminated Li-mica with K{sup +}. The CEC of this K-mica was determined by exchanging its surface cations with Cs{sup +}, NH{sub 4}{sup +}, methylene blue (MB{sup +}), and copper triethylenetetramine [Cu(trien){sup 2+}]. The kinetics of these exchange reactions were studied and showed large differences depending on their relative affinities to mica. The NH{sub 4}{sup +}/K{sup +} exchange was slow, while the Cs{sup +} and Cu(trien){sup 2+}/K{sup +} exchange was fast. The MB{sup +}/K{sup +} exchange was quite slow and was not completed even after 99 h. Insufficient reaction time is one of the main reasons for the contradictory results reported in the literature for the CEC of aluminosilicates obtained by different methods. The CEC of mica can be photometrically measured by exchanging its surface cations with Cu(trien){sup 2+}.

  2. Ab initio study of the phenol-water cation radical

    NASA Astrophysics Data System (ADS)

    Hobza, Pavel; Burcl, Rudolf; Špirko, Vladimír; Dopfer, Otto; Müller-Dethlefs, Klaus; Schlag, Edward W.

    1994-07-01

    The phenol-water cation radical has been investigated by ab initio theory using the spin-restricted open-shell Hartree-Fock and spin-restricted open-shell second-order Møller-Plesset theories with 3-21G*(O) and 6-31G* basis sets. The full geometrical optimization was performed for several hydrogen-bonded structures and one hemibonded structure. Clearly, the most stable structure has been found for Cs symmetry with the linear hydrogen bond between the proton of the OH group of the phenol cation radical and the oxygen of the water, and the water hydrogens pointing away from the phenyl ring. For this structure harmonic (and for some intermolecular modes anharmonic) vibrational frequencies have been computed for various isotopic complexes. The computed shifts of phenol-localized intramolecular modes on complexation and on deuteration as well as the calculated intermolecular frequencies of the different isotopic complexes allow for an assignment of vibrational frequencies observed in the experimental zero-kinetic-energy (ZEKE) photoelectron spectra. Five out of a possible six intermolecular vibrations and several intramolecular modes have been assigned, including the 18b vibration which shows a strong blue shift in frequency upon complexation. Structure and properties of the phenol-water cation radical are compared with those of the corresponding neutral complex.

  3. Drug loading to lipid-based cationic nanoparticles

    NASA Astrophysics Data System (ADS)

    Cavalcanti, Leide P.; Konovalov, Oleg; Torriani, Iris L.; Haas, Heinrich

    2005-08-01

    Lipid-based cationic nanoparticles are a new promising option for tumor therapy, because they display enhanced binding and uptake at the neo-angiogenic endothelial cells, which a tumor needs for its nutrition and growth. By loading suitable cytotoxic compounds to the cationic carrier, the tumor endothelial and consequently also the tumor itself can be destroyed. For the development of such novel anti-tumor agents, the control of drug loading and drug release from the carrier matrix is essential. We have studied the incorporation of the hydrophobic anti-cancer agent Paclitaxel (PXL) into a variety of lipid matrices by X-Ray reflectivity measurements. Liposome suspensions from cationic and zwitterionic lipids, comprising different molar fractions of Paclitaxel, were deposited on planar glass substrates. After drying at controlled humidity, well ordered, oriented multilayer stacks were obtained, as proven by the presence of bilayer Bragg peaks to several orders in the reflectivity curves. The presence of the drug induced a decrease of the lipid bilayer spacing, and with an excess of drug, also Bragg peaks of drug crystals could be observed. From the results, insight into the solubility of Paclitaxel in the model membranes was obtained and a structural model of the organization of the drug in the membrane was derived. Results from subsequent pressure/area-isotherm and grazing incidence diffraction (GID) measurements performed with drug/lipid Langmuir monolayers were in accordance with these conjectures.

  4. Nucleophilic addition of nitrogen to aryl cations: mimicking Titan chemistry.

    PubMed

    Li, Anyin; Jjunju, Fred P M; Cooks, R Graham

    2013-11-01

    The reactivity of aryl cations toward molecular nitrogen is studied systematically in an ion trap mass spectrometer at 10(2) Pascal of nitrogen, the pressure of the Titan main haze layer. Nucleophilic addition of dinitrogen occurs and the nature of aryl group has a significant influence on the reactivity, through inductive effects and by changing the ground state spin multiplicity. The products of nitrogen activation, aryldiazonium ions, react with typical nitriles, aromatic amines, and alkynes (compounds that are relevant as possible Titan atmosphere constituents) to form covalently bonded heterocyclic products. Theoretical calculations at the level [DFT(B3LYP)/6-311++G(d,p)] indicate that the N2 addition reaction is exothermic for the singlet aryl cations but endothermic for their triplet spin isomers. The -OH and -NH2 substituted aryl ions are calculated to have triplet ground states, which is consistent with their decreased nitrogen addition reactivity. The energy needed for the generation of the aryl cations from their protonated precursors (ca. 340 kJ/mol starting with protonated aniline) is far less than that required to directly activate the nitrogen triple bond (the lowest energy excited state of N2 lies ca. 600 kJ/mol above the ground state). The formation of aza-aromatics via arene ionization and subsequent reactions provide a conceivable route to the genesis of nitrogen-containing organic molecules in the interstellar medium and Titan haze layers. PMID:23982933

  5. Transformation of anthracene on various cation-modified clay minerals.

    PubMed

    Li, Li; Jia, Hanzhong; Li, Xiyou; Wang, Chuanyi

    2015-01-01

    In this study, anthracene was employed as a probe to explore the potential catalytic effect of clay minerals in soil environment. Clay minerals saturated with various exchangeable cations were tested. The rate of anthracene transformation follows the order: Fe-smectite > Cu-smectite > Al-smectite ≈ Ca-smectite ≈ Mg-smectite ≈ Na-smectite. This suggests that transition-metal ions such as Fe(III) play an important role in anthracene transformation. Among Fe(III)-saturated clays, Fe(III)-smectite exhibits the highest catalytic activity followed by Fe(III)-illite, Fe(III)-pyrophyllite, and Fe(III)-kaolinite, which is in agreement with the interlayer Fe(III) content. Moreover, effects by two common environmental factors, pH and relative humidity (RH), were evaluated. With an increase in pH or RH, the rate of anthracene transformation decreases rapidly at first and then is leveled off. GC-MS analysis identifies that the final product of anthracene transformation is 9,10-anthraquinone, a more bioavailable molecule compared to anthracene. The transformation process mainly involves cation-π bonding, electron transfer leading to cation radical, and further oxidation by chemisorbed O2. The present work provides valuable insights into the abiotic transformation and the fate of PAHs in the soil environment and the development of contaminated land remediation technologies. PMID:25135171

  6. Solubility and transport of cationic and anionic patterned nanoparticles

    NASA Astrophysics Data System (ADS)

    Su, Jiaye; Olvera de La Cruz, Monica; Guo, Hongxia

    2012-01-01

    We analyze bulk diffusion and transport through hydrophobic nanochannels of nanoparticles (NPs) with different hydrophobic-hydrophilic patterns achieved by coating a fraction of the NP sites with positive or negative charges via explicit solvent molecular dynamics simulations. Ten different charge pattern types including Janus charged-hydrophobic NPs are studied. The cationic NPs are more affected by the patterns and have higher diffusion constants and fluxes than their anionic NPs counterparts. The NP-water interaction dependence on surface pattern and field strength explains these observations. The NP-water Coulomb interaction of anionic NPs in the bulk, which are much stronger than the hydrophobic NP-water interactions, are stronger for NPs with higher localized charge, and stronger than in the cationic NPs counterparts. The diffusion and transport of anionic NPs such as proteins and protein charge ladders with the same total charge but different surface charge patterns are slowest for the highest localized charge pattern, which also adsorb strongest onto surfaces. Our model demonstrates the separation (by reverse osmosis, capillary electrophoresis, or chromatography) of cationic NPs, including proteins with equal net charge but different surface charge distributions.

  7. Biocidal activity of some Mannich base cationic derivatives.

    PubMed

    Negm, Nabel A; Morsy, Salwa M I; Said, Medhat M

    2005-11-01

    A novel series of cationic surfactants was prepared based on Mannich base (produced from the condensation of piperidine and/or morpholine as secondary amine and paraformaldehyde in the presence of 8-hydroxyquinoline). The chemical structures of the synthesized cationic surfactants were confirmed using elemental analyses, FTIR spectroscopy and 1H NMR. Surface activities of the prepared surfactants were measured including: surface tension (gamma), critical micelle concentration (CMC), effectiveness (pi(CMC)), efficiency (Pc20), maximum surface excess (Gamma(max)), minimum surface area (A(min)), interfacial tension (gamma(IT)), emulsification power and foaming power at 25 degrees C. The structural influences on their surface activities and adsorption free energy were discussed. The synthesized cationic surfactants were evaluated for their biocidal activity towards Gram +ve bacteria (Staph. Cocu., Bacillus), Gram -ve bacteria (Salmonella, E. coli), fungi (A. terrus., A. flav.) and yeast (Candida) at 1.0, 2.5 and 5.0mg/mL, respectively. The target compounds showed good inhibition towards Gram +ve bacteria, Gram -ve bacteria and yeast. Meanwhile, excellent fungicidal results were obtained against the various types of fungi under investigation. PMID:16154748

  8. Electron exchange involving a sulfur-stabilized ruthenium radical cation.

    PubMed

    Shaw, Anthony P; Ryland, Bradford L; Norton, Jack R; Buccella, Daniela; Moscatelli, Alberto

    2007-07-01

    Half-sandwich Ru(II) amine, thiol, and thiolate complexes were prepared and characterized by X-ray crystallography. The thiol and amine complexes react slowly with acetonitrile to give free thiol or amine and the acetonitrile complex. With the thiol complex, the reaction is dissociative. The thiolate complex has been oxidized to its Ru(III) radical cation and the solution EPR spectrum of that radical cation recorded. Cobaltocene reduces the thiol complex to the thiolate complex. The 1H and 31P NMR signals of the thiolate complex in acetonitrile become very broad whenever the thiolate and thiol complexes are present simultaneously. The line broadening is primarily due to electron exchange between the thiolate complex and its radical cation; the latter is generated by an unfavorable redox equilibrium between the thiol and thiolate complexes. Pyramidal inversion of sulfur in the thiol complex is fast at room temperature but slow at lower temperatures; major and minor conformers of the thiol complex were observed by 31P NMR at -98 degrees C in CD2Cl2. PMID:17569530

  9. Bioaccumulation and toxicity of a cationic surfactant (DODMAC) in sediment dwelling freshwater invertebrates.

    PubMed

    Comber, S D W; Rule, K L; Conrad, A U; Höss, S; Webb, S F; Marshall, S

    2008-05-01

    Dimethyldioctadecylammonium chloride (DODMAC, CAS No. 107-64-2) is the principal active component of Di(hydrogenated tallow alkyl) dimethylammonium chloride (DHTDMAC, CAS No. 61789-80-8), a cationic surfactant formerly used principally in laundry fabric softeners. After discharge to water, DODMAC partitions strongly to sediment, therefore the assessment of the effects of DODMAC to benthic organisms is essential in any risk assessment. Chronic toxicity studies were conducted with Lumbriculus variegatus (Oligochaete), Tubifex tubifex (Oligochaete) and Caenorhabditis elegans (Nematode). NOECs were greater than 5738, 1515 and 1351 mg/kg dw, respectively, even for sub-lethal effects. Measurement of the route of uptake of DODMAC by L. variegatus demonstrated the relative importance of uptake via ingestion (86%) compared with direct contact with the sediment and via pore water (14%). The overall tendency of DODMAC to bioaccumulate, however, was low with measured accumulation factors of 0.22 and 0.78 for L. variegatus and T. tubifex, respectively. PMID:17889974

  10. Phospholamban spontaneously reconstitutes into giant unilamellar vesicles where it generates a cation selective channel.

    PubMed

    Smeazzetto, S; Tadini-Buoninsegni, F; Thiel, G; Berti, D; Montis, C

    2016-01-21

    Phospholamban (PLN) is a small integral membrane protein, which modulates the activity of the Sarcoplasmic Reticulum Ca(2+)-ATPase (SERCA) of cardiac myocytes. PLN, as a monomer, can directly interact and tune SERCA activity, but the physiological function of the pentameric form is not yet fully understood and still debated. In this work, we reconstituted PLN in Giant Unilamellar Vesicles (GUVs), a simple and reliable experimental model system to monitor the activity of proteins in membranes. By Laser Scanning Confocal Microscopy (LSCM) and Fluorescence Correlation Spectroscopy (FCS) we verified a spontaneous reconstitution of PLN into the phospholipid bilayer. In parallel experiments, we measured with the patch clamp technique canonical ion channel fluctuations, which highlight a preference for Cs(+) over K(+) and do not conduct Ca(2+). The results prove that PLN forms, presumably in its pentameric form, a cation selective ion channel. PMID:26673394

  11. Binding of monovalent metal cations by the p-sulfonatocalix[4]arene: experimental evidence for cation-pi interactions in water.

    PubMed

    Morel, Jean-Pierre; Morel-Desrosiers, Nicole

    2006-02-01

    Gibbs free energies, enthalpies and entropies for the binding of Na+, K+, Rb+, Cs+, Ag+, Tl+ and NH4+ by the p-sulfonatocalix[4]arene in water are determined by microcalorimetry. Whereas no significant heat effect is detected with Na+ or Ag+, suggesting that these cations are not complexed, weak but selective binding is observed with the other cations. The whole set of thermodynamic parameters, which demonstrate that the cations bind inside the cavity of the calixarene, evidence the importance of the cation-pi interactions for these complexes in water. PMID:16446803

  12. Ionic surface electrical conductivity in sandstone

    NASA Astrophysics Data System (ADS)

    Glover, Paul W. J.; Meredith, Philip G.; Sammonds, Peter R.; Murrell, Stanley A. F.

    1994-11-01

    Recent analyses of complex conductivity measurements have indicated that high-frequency dispersions encountered in rocks saturated with low-salinity fluids are due to ionic surface conduction and that the form of these dispersions may be dependent upon the nature of the pore and crack surfaces within the rock (Ruffet et al., 1991). Unfortunately, the mechanisms of surface conduction are not well understood, and no model based on rigorous physical principles exists. This paper is split into two parts: an experimental section followed by the development of a theoretical description of adsorption of ions onto mineral surfaces. We have made complex conductivity measurements upon samples of sandstone saturated with a range of different types and concentrations of aqueous solution with a frequency range of 20 Hz to 1 MHz. The frequency dependence of complex conductivity was analyzed using the empirical model of Cole and Cole (1941). The 'fractal' surface models of Le Mehaute and Crepy (1983), Po Zen Wong (1987), the Ruffet el at. (1991) were used to calculate apparent fractal pore surface dimensions for samples saturated with different solution types and concentrations. These showed a pronounced decrease of apparent fractal surface dimension with decreasing electrolyte concentration and a decrease of apparent fractal dimension with increasing relative ionic radius of the dominant cation in solution. A model for ionic surface concentration (ISCOM I) has been developed as the first step in producing a rigorous physicochemical model of surface conduction in quartz-dominated rocks. The results from ISCOM I show that quartz surfaces are overwhelmingly dominated by adsorbed Na(+) when saturated with NaCl solutions of salinities and pH found in actual geological situations. ISCOM I also shows that the concentration threshold for dominance of surface conduction over bulk conduction is aided by depletion of ions from the bulk fluid as a result of their adsorption onto the mineral

  13. Transparent conducting oxide nanotubes

    NASA Astrophysics Data System (ADS)

    Alivov, Yahya; Singh, Vivek; Ding, Yuchen; Nagpal, Prashant

    2014-09-01

    Thin film or porous membranes made of hollow, transparent, conducting oxide (TCO) nanotubes, with high chemical stability, functionalized surfaces and large surface areas, can provide an excellent platform for a wide variety of nanostructured photovoltaic, photodetector, photoelectrochemical and photocatalytic devices. While large-bandgap oxide semiconductors offer transparency for incident light (below their nominal bandgap), their low carrier concentration and poor conductivity makes them unsuitable for charge conduction. Moreover, materials with high conductivity have nominally low bandgaps and hence poor light transmittance. Here, we demonstrate thin films and membranes made from TiO2 nanotubes heavily-doped with shallow Niobium (Nb) donors (up to 10%, without phase segregation), using a modified electrochemical anodization process, to fabricate transparent conducting hollow nanotubes. Temperature dependent current-voltage characteristics revealed that TiO2 TCO nanotubes, doped with 10% Nb, show metal-like behavior with resistivity decreasing from 6.5 × 10-4 Ωcm at T = 300 K (compared to 6.5 × 10-1 Ωcm for nominally undoped nanotubes) to 2.2 × 10-4 Ωcm at T = 20 K. Optical properties, studied by reflectance measurements, showed light transmittance up to 90%, within wavelength range 400 nm-1000 nm. Nb doping also improves the field emission properties of TCO nanotubes demonstrating an order of magnitude increase in field-emitter current, compared to undoped samples.

  14. Transparent conducting oxide nanotubes.

    PubMed

    Alivov, Yahya; Singh, Vivek; Ding, Yuchen; Nagpal, Prashant

    2014-09-26

    Thin film or porous membranes made of hollow, transparent, conducting oxide (TCO) nanotubes, with high chemical stability, functionalized surfaces and large surface areas, can provide an excellent platform for a wide variety of nanostructured photovoltaic, photodetector, photoelectrochemical and photocatalytic devices. While large-bandgap oxide semiconductors offer transparency for incident light (below their nominal bandgap), their low carrier concentration and poor conductivity makes them unsuitable for charge conduction. Moreover, materials with high conductivity have nominally low bandgaps and hence poor light transmittance. Here, we demonstrate thin films and membranes made from TiO2 nanotubes heavily-doped with shallow Niobium (Nb) donors (up to 10%, without phase segregation), using a modified electrochemical anodization process, to fabricate transparent conducting hollow nanotubes. Temperature dependent current-voltage characteristics revealed that TiO2 TCO nanotubes, doped with 10% Nb, show metal-like behavior with resistivity decreasing from 6.5 × 10(-4) Ωcm at T = 300 K (compared to 6.5 × 10(-1) Ωcm for nominally undoped nanotubes) to 2.2 × 10(-4) Ωcm at T = 20 K. Optical properties, studied by reflectance measurements, showed light transmittance up to 90%, within wavelength range 400 nm-1000 nm. Nb doping also improves the field emission properties of TCO nanotubes demonstrating an order of magnitude increase in field-emitter current, compared to undoped samples. PMID:25180635

  15. Cartilage conduction hearing.

    PubMed

    Shimokura, Ryota; Hosoi, Hiroshi; Nishimura, Tadashi; Yamanaka, Toshiaki; Levitt, Harry

    2014-04-01

    Sound information is known to travel to the cochlea via either air or bone conduction. However, a vibration signal, delivered to the aural cartilage via a transducer, can also produce a clearly audible sound. This type of conduction has been termed "cartilage conduction." The aural cartilage forms the outer ear and is distributed around the exterior half of the external auditory canal. In cartilage conduction, the cartilage and transducer play the roles of a diaphragm and voice coil of a loudspeaker, respectively. There is a large gap between the impedances of cartilage and skull bone, such that cartilage vibrations are not easily transmitted through bone. Thus, these methods of conduction are distinct. In this study, force was used to apply a transducer to aural cartilage, and it was found that the sound in the auditory canal was amplified, especially for frequencies below 2 kHz. This effect was most pronounced at an application force of 1 N, which is low enough to ensure comfort in the design of hearing aids. The possibility of using force adjustments to vary amplification may also have applications for cell phone design. PMID:25234994

  16. Resorcarene-based receptor: versatile behavior in its interaction with heavy and soft metal cations.

    PubMed

    Danil de Namor, Angela F; Chaaban, Jinane K; Piro, Oscar E; Castellano, Eduardo E

    2006-02-01

    Standard solution Gibbs energies, DeltasG degrees, of the resorcarene-based receptor 5,11,17,23-ethylthiomethylated calix[4]resorcarene, (characterized by 1H NMR and X-ray diffraction studies) in its monomeric state (established through partition experiments) in various solvents are for the first time reported in the area of resorcarene chemistry. Transfer Gibbs energies of from hexane (reference solvent) to other medium are calculated. Agreement between DeltatG degrees (referred to the pure solvents) and standard partition Gibbs energies, DeltapG degrees (solvent mutually saturated) is found. Cation-ligand interactions were investigated through 1H NMR (CD3CN and CD3OD) and conductometric titrations in acetonitrile and methanol. 1H NMR data revealed the sites of interaction of with the metal cation. The composition of the metal-ion complexes (Ag+ and Pb2+ in acetonitrile and Ag+ and Cu2+ in methanol) was established through conductometric titrations. Thus, complexes of 1:1 stoichiometry were formed between and Ag+ and Pb2+ in acetonitrile and Cu2+ in methanol. However, in moving from acetonitrile to methanol, the composition of the silver complex was altered. Thus, two metal cations are hosted by a unit of the ligand. As far as Cu2+ and in acetonitrile is concerned, conductance data suggest that metalates are formed in which up to four units of Cu2+ are taken up per unit of resorcarene. The contrasting behavior of with Cu2+ in acetonitrile relative to methanol is discussed. As far as mercury (II) is concerned, the unusual jump in conductance observed in the titration of Hg2+ with in acetonitrile and methanol after the formation of a multicharged complex (undefined composition) is attributed to the presence of highly charged smaller units (higher mobility) resulting from the departure of pendant arms from the resorcarene backbone. Isolation of these species followed by X-ray diffraction studies corroborated this statement. The thermodynamic characterization of metal

  17. The electronic structures of vanadate salts: Cation substitution as a tool for band gap manipulation

    NASA Astrophysics Data System (ADS)

    Dolgos, Michelle R.; Paraskos, Alexandra M.; Stoltzfus, Matthew W.; Yarnell, Samantha C.; Woodward, Patrick M.

    2009-07-01

    The electronic structures of six ternary metal oxides containing isolated vanadate ions, Ba 3(VO 4) 2, Pb 3(VO 4) 2, YVO 4, BiVO 4, CeVO 4 and Ag 3VO 4 were studied using diffuse reflectance spectroscopy and electronic structure calculations. While the electronic structure near the Fermi level originates largely from the molecular orbitals of the vanadate ion, both experiment and theory show that the cation can strongly influence these electronic states. The observation that Ba 3(VO 4) 2 and YVO 4 have similar band gaps, both 3.8 eV, shows that cations with a noble gas configuration have little impact on the electronic structure. Band structure calculations support this hypothesis. In Pb 3(VO 4) 2 and BiVO 4 the band gap is reduced by 0.9-1.0 eV through interactions of (a) the filled cation 6 s orbitals with nonbonding O 2 p states at the top of the valence band, and (b) overlap of empty 6 p orbitals with antibonding V 3 d-O 2 p states at the bottom of the conduction band. In Ag 3VO 4 mixing between filled Ag 4 d and O 2 p states destabilizes states at the top of the valence band leading to a large decrease in the band gap ( Eg=2.2 eV). In CeVO 4 excitations from partially filled 4 f orbitals into the conduction band lower the effective band gap to 1.8 eV. In the Ce 1-xBi xVO 4 (0≤ x≤0.5) and Ce 1-xY xVO 4 ( x=0.1, 0.2) solid solutions the band gap narrows slightly when Bi 3+ or Y 3+ are introduced. The nonlinear response of the band gap to changes in composition is a result of the localized nature of the Ce 4 f orbitals.

  18. Ionic conductivity studies of gel polyelectrolyte based on ionic liquid

    NASA Astrophysics Data System (ADS)

    Cha, E. H.; Lim, S. A.; Park, J. H.; Kim, D. W.; Macfarlane, D. R.

    Novel lithium polyelectrolyte-ionic liquids have been prepared and characterized of their properties. Poly(lithium 2-acrylamido-2-methyl propanesulfonate) (PAMPSLi) and its copolymer with N-vinyl formamide (VF) also has been prepared as a copolymer. 1-Ethyl-3-methylimidazolium tricyanomethanide (emImTCM) and N, N-dimethyl- N-propyl- N-butyl ammonium tricyanomethanide (N 1134TCM) which are chosen because of the same with the anion of ionic liquid were prepared. The ionic conductivity of copolymer system (PAMPSLi/PVF/emImTCM: 5.43 × 10 -3 S cm -1 at 25 °C) exhibits about over four times higher than that of homopolymer system (PAMPSLi/emImTCM: 1.28 × 10 -3 S cm -1 at 25 °C). Introduction of vinyl formamide into the copolymer type can increase the dissociation of the lithium cations from the polymer backbone. The ionic conductivity of copolymer with emImTCM (PAMPSLi/PVF/emImTCM) exhibits the higher conductivity than that of PAMPSLi/PVF/N 1134TCM (2.48 × 10 -3 S cm -1). Because of using the polymerizable anion it is seen to maintain high flexibility of imidazolium cation effectively to exhibit the higher conductivity. And also the viscosity of emImTCM (19.56 cP) is lower than that of N 1134TCM (28.61 cP). Low viscosity leads to a fast rate of diffusion of redox species.

  19. Conduction Mechanisms and Structure of Ionomeric Single-Ion Conductors

    SciTech Connect

    Colby, Ralph H.; Maranas, Janna K; Mueller, Karl T; Runt, James; Winey, Karen I

    2015-03-05

    Our team has designed using DFT (Gaussian) and synthesized low glass transition temperature single-ion conductors that are either polyanions that conduct small cations Li, Na, Cs or polycations that conduct small anions F, OH, Br. We utilize a wide range of complimentary experimental materials charactization tools to understand ion transport; differential scanning calorimetry, dielectric relaxation spectroscopy, infrared spectroscopy, nuclear magnetic resonance spectroscopy, linear viscoelasticity, X-ray scattering and molecular dynamics simulations. The glass transition temperature Tg needs to be as low as possible to facilitate ion transport, so the nonionic parts of the polymer need to be polar, flexible and have strong solvation interactions with the ions. The lowest Tg we have managed for polyanions conducting Li is -60 C. In contrast, polysiloxanes with PEO side chains and tetrabutylphosphonium cationic side groups have Tg ~ -75C that barely increases with ion content, as anticipated by DFT. A survey of all polyanions in the literature suggests that Tg < -80C is needed to achieve the 10-4 S/cm conductivity needed for battery separators.

  20. Proliferating conduction by isomerism

    NASA Astrophysics Data System (ADS)

    Kaur, Rupan Preet; Sawhney, Ravinder Singh; Engles, Derick

    2015-01-01

    The electrical conduction of isomers of anthracene molecule attached between two semi-infinite gold electrodes was simulated using extended Huckel theory (EHT)-based on semi-empirical model in this research work. The electron transport parameters were examined in two epochs by buffering anthracene and its isomer phenanthrene alternatively between gold electrodes using sulphur as an alligator clip, under variegated bias voltages. Differential NDR effect was observed in both the cases but phenanthrene exhibited more linear I-V curve than its counterpart, anthracene. The simulated results discovered phenanthrene as a better candidate than anthracene towards contributing to electrical conduction in molecular junctions. Phenanthrene reported maximum conductance of 0.74G0 whereas anthracene exhibited 0.03G0 at 0.8V.