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Sample records for cation diffusion facilitator

  1. Disease-Homologous Mutation in the Cation Diffusion Facilitator Protein MamM Causes Single-Domain Structural Loss and Signifies Its Importance.

    PubMed

    Barber-Zucker, Shiran; Uebe, René; Davidov, Geula; Navon, Yotam; Sherf, Dror; Chill, Jordan H; Kass, Itamar; Bitton, Ronit; Schüler, Dirk; Zarivach, Raz

    2016-01-01

    Cation diffusion facilitators (CDF) are highly conserved, metal ion efflux transporters that maintain divalent transition metal cation homeostasis. Most CDF proteins contain two domains, the cation transporting transmembrane domain and the regulatory cytoplasmic C-terminal domain (CTD). MamM is a magnetosome-associated CDF protein essential for the biomineralization of magnetic iron-oxide particles in magnetotactic bacteria. To investigate the structure-function relationship of CDF cytoplasmic domains, we characterized a MamM M250P mutation that is synonymous with the disease-related mutation L349P of the human CDF protein ZnT-10. Our results show that the M250P exchange in MamM causes severe structural changes in its CTD resulting in abnormal reduced function. Our in vivo, in vitro and in silico studies indicate that the CTD fold is critical for CDF proteins' proper function and support the previously suggested role of the CDF cytoplasmic domain as a CDF regulatory element. Based on our results, we also suggest a mechanism for the effects of the ZnT-10 L349P mutation in human. PMID:27550551

  2. Disease-Homologous Mutation in the Cation Diffusion Facilitator Protein MamM Causes Single-Domain Structural Loss and Signifies Its Importance

    PubMed Central

    Barber-Zucker, Shiran; Uebe, René; Davidov, Geula; Navon, Yotam; Sherf, Dror; Chill, Jordan H.; Kass, Itamar; Bitton, Ronit; Schüler, Dirk; Zarivach, Raz

    2016-01-01

    Cation diffusion facilitators (CDF) are highly conserved, metal ion efflux transporters that maintain divalent transition metal cation homeostasis. Most CDF proteins contain two domains, the cation transporting transmembrane domain and the regulatory cytoplasmic C-terminal domain (CTD). MamM is a magnetosome-associated CDF protein essential for the biomineralization of magnetic iron-oxide particles in magnetotactic bacteria. To investigate the structure-function relationship of CDF cytoplasmic domains, we characterized a MamM M250P mutation that is synonymous with the disease-related mutation L349P of the human CDF protein ZnT-10. Our results show that the M250P exchange in MamM causes severe structural changes in its CTD resulting in abnormal reduced function. Our in vivo, in vitro and in silico studies indicate that the CTD fold is critical for CDF proteins’ proper function and support the previously suggested role of the CDF cytoplasmic domain as a CDF regulatory element. Based on our results, we also suggest a mechanism for the effects of the ZnT-10 L349P mutation in human. PMID:27550551

  3. 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

  4. Cation self-diffusion in Fe2O3

    NASA Astrophysics Data System (ADS)

    Hoshino, K.; Peterson, N. L.

    Self-diffusion of Fe(59) in single crystals of Fe2O3 parallel to the c-axis has been measured as a function of temperature (1150 to 1340 C) and oxygen partial pressure 0.002 less than or equal to Po2 less than or equal to 1 atm). The oxygen partial pressure dependence of the diffusivity indicates that cation self-diffusion occurs by an interstitial-type mechanism. The simultaneous diffusion of Fe(52) and Fe(59) was measured in Fe2O3 at 1251 C and Po2 = .0191 atm. The small value of the isotope effect (f(DELTA)K = 0.067 + or - 0.016) is consistent with diffusion of Fe ions by an interstitially mechanism.

  5. Role of Reverse Divalent Cation Diffusion in Forward Osmosis Biofouling.

    PubMed

    Xie, Ming; Bar-Zeev, Edo; Hashmi, Sara M; Nghiem, Long D; Elimelech, Menachem

    2015-11-17

    We investigated the role of reverse divalent cation diffusion in forward osmosis (FO) biofouling. FO biofouling by Pseudomonas aeruginosa was simulated using pristine and chlorine-treated thin-film composite polyamide membranes with either MgCl2 or CaCl2 draw solution. We related FO biofouling behavior-water flux decline, biofilm architecture, and biofilm composition-to reverse cation diffusion. Experimental results demonstrated that reverse calcium diffusion led to significantly more severe water flux decline in comparison with reverse magnesium permeation. Unlike magnesium, reverse calcium permeation dramatically altered the biofilm architecture and composition, where extracellular polymeric substances (EPS) formed a thicker, denser, and more stable biofilm. We propose that FO biofouling was enhanced by complexation of calcium ions to bacterial EPS. This hypothesis was confirmed by dynamic and static light scattering measurements using extracted bacterial EPS with the addition of either MgCl2 or CaCl2 solution. We observed a dramatic increase in the hydrodynamic radius of bacterial EPS with the addition of CaCl2, but no change was observed after addition of MgCl2. Static light scattering revealed that the radius of gyration of bacterial EPS with addition of CaCl2 was 20 times larger than that with the addition of MgCl2. These observations were further confirmed by transmission electron microscopy imaging, where bacterial EPS in the presence of calcium ions was globular, while that with magnesium ions was rod-shaped.

  6. Role of Reverse Divalent Cation Diffusion in Forward Osmosis Biofouling.

    PubMed

    Xie, Ming; Bar-Zeev, Edo; Hashmi, Sara M; Nghiem, Long D; Elimelech, Menachem

    2015-11-17

    We investigated the role of reverse divalent cation diffusion in forward osmosis (FO) biofouling. FO biofouling by Pseudomonas aeruginosa was simulated using pristine and chlorine-treated thin-film composite polyamide membranes with either MgCl2 or CaCl2 draw solution. We related FO biofouling behavior-water flux decline, biofilm architecture, and biofilm composition-to reverse cation diffusion. Experimental results demonstrated that reverse calcium diffusion led to significantly more severe water flux decline in comparison with reverse magnesium permeation. Unlike magnesium, reverse calcium permeation dramatically altered the biofilm architecture and composition, where extracellular polymeric substances (EPS) formed a thicker, denser, and more stable biofilm. We propose that FO biofouling was enhanced by complexation of calcium ions to bacterial EPS. This hypothesis was confirmed by dynamic and static light scattering measurements using extracted bacterial EPS with the addition of either MgCl2 or CaCl2 solution. We observed a dramatic increase in the hydrodynamic radius of bacterial EPS with the addition of CaCl2, but no change was observed after addition of MgCl2. Static light scattering revealed that the radius of gyration of bacterial EPS with addition of CaCl2 was 20 times larger than that with the addition of MgCl2. These observations were further confirmed by transmission electron microscopy imaging, where bacterial EPS in the presence of calcium ions was globular, while that with magnesium ions was rod-shaped. PMID:26503882

  7. 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.

  8. Cationic Peptides Facilitate Iron-induced Mutagenesis in Bacteria

    PubMed Central

    Rodríguez-Rojas, Alexandro; Makarova, Olga; Müller, Uta; Rolff, Jens

    2015-01-01

    Pseudomonas aeruginosa is the causative agent of chronic respiratory infections and is an important pathogen of cystic fibrosis patients. Adaptive mutations play an essential role for antimicrobial resistance and persistence. The factors that contribute to bacterial mutagenesis in this environment are not clear. Recently it has been proposed that cationic antimicrobial peptides such as LL-37 could act as mutagens in P. aeruginosa. Here we provide experimental evidence that mutagenesis is the product of a joint action of LL-37 and free iron. By estimating mutation rate, mutant frequencies and assessing mutational spectra in P. aeruginosa treated either with LL-37, iron or a combination of both we demonstrate that mutation rate and mutant frequency were increased only when free iron and LL-37 were present simultaneously. Colistin had the same effect. The addition of an iron chelator completely abolished this mutagenic effect, suggesting that LL-37 enables iron to enter the cells resulting in DNA damage by Fenton reactions. This was also supported by the observation that the mutational spectrum of the bacteria under LL-37-iron regime showed one of the characteristic Fenton reaction fingerprints: C to T transitions. Free iron concentration in nature and within hosts is kept at a very low level, but the situation in infected lungs of cystic fibrosis patients is different. Intermittent bleeding and damage to the epithelial cells in lungs may contribute to the release of free iron that in turn leads to generation of reactive oxygen species and deterioration of the respiratory tract, making it more susceptible to the infection. PMID:26430769

  9. Facilitated Diffusion as a Method for Selective Accumulation of Materials from the Primordial Oceans by a Lipid Vesicle Protocell

    NASA Astrophysics Data System (ADS)

    Stillwell, William

    1980-09-01

    A model is proposed for the selective accumulation of amino acids, sugars, nucleotides, cations and protons from the primordial oceans into a lipid vesicle type of protocell. The model is built on facilitated diffusion using simple, primordial, lipid-soluble carriers. The advantages a lipid vesicle protocell would have had over the other potential types of protocells are discussed.

  10. Facilitated diffusion of proteins through crumpled fractal DNA globules

    NASA Astrophysics Data System (ADS)

    Smrek, Jan; Grosberg, Alexander Y.

    2015-07-01

    We explore how the specific fractal globule conformation, found for the chromatin fiber of higher eukaryotes and topologically constrained dense polymers, affects the facilitated diffusion of proteins in this environment. Using scaling arguments and supporting Monte Carlo simulations, we relate DNA looping probability distribution, fractal dimension, and protein nonspecific affinity for the DNA to the effective diffusion parameters of the proteins. We explicitly consider correlations between subsequent readsorption events of the proteins, and we find that facilitated diffusion is faster for the crumpled globule conformation with high intersegmental surface dimension than in the case of dense fractal conformations with smooth surfaces. As a byproduct, we obtain an expression for the macroscopic conductivity of a hypothetic material consisting of conducting fractal nanowires immersed in a weakly conducting medium.

  11. Facilitated diffusion of proteins through crumpled fractal DNA globules.

    PubMed

    Smrek, Jan; Grosberg, Alexander Y

    2015-07-01

    We explore how the specific fractal globule conformation, found for the chromatin fiber of higher eukaryotes and topologically constrained dense polymers, affects the facilitated diffusion of proteins in this environment. Using scaling arguments and supporting Monte Carlo simulations, we relate DNA looping probability distribution, fractal dimension, and protein nonspecific affinity for the DNA to the effective diffusion parameters of the proteins. We explicitly consider correlations between subsequent readsorption events of the proteins, and we find that facilitated diffusion is faster for the crumpled globule conformation with high intersegmental surface dimension than in the case of dense fractal conformations with smooth surfaces. As a byproduct, we obtain an expression for the macroscopic conductivity of a hypothetic material consisting of conducting fractal nanowires immersed in a weakly conducting medium.

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

    NASA Technical Reports Server (NTRS)

    Good, Brian

    2011-01-01

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

  13. Electrochemistry of cations in diopsidic melt - Determining diffusion rates and redox potentials from voltammetric curves

    NASA Technical Reports Server (NTRS)

    Colson, Russell O.; Haskin, Larry A.; Crane, Daniel

    1990-01-01

    Results are presented on determinations of reduction potentials and their temperature dependence of selected ions in diopsidic melt, by using linear sweep voltammetry. Diffusion coefficients were measured for cations of Eu, Mn, Cr, and In. Enthalpies and entropies of reduction were determined for the cations V(V), Cr(3+), Mn(2+), Mn(3+), Fe(2+), Cu(2+), Mo(VI), Sn(IV), and Eu(3+). Reduction potentials were used to study the structural state of cations in the melt.

  14. Probing the DNA structural requirements for facilitated diffusion.

    PubMed

    Hedglin, Mark; Zhang, Yaru; O'Brien, Patrick J

    2015-01-20

    DNA glycosylases perform a genome-wide search to locate damaged nucleotides among a great excess of undamaged nucleotides. Many glycosylases are capable of facilitated diffusion, whereby multiple sites along the DNA are sampled during a single binding encounter. Electrostatic interactions between positively charged amino acids and the negatively charged phosphate backbone are crucial for facilitated diffusion, but the extent to which diffusing proteins rely on the double-helical structure DNA is not known. Kinetic assays were used to probe the DNA searching mechanism of human alkyladenine DNA glycosylase (AAG) and to test the extent to which diffusion requires B-form duplex DNA. Although AAG excises εA lesions from single-stranded DNA, it is not processive on single-stranded DNA because dissociation is faster than N-glycosidic bond cleavage. However, the AAG complex with single-stranded DNA is sufficiently stable to allow for DNA annealing when a complementary strand is added. This observation provides evidence of nonspecific association of AAG with single-stranded DNA. Single-strand gaps, bubbles, and bent structures do not impede the search by AAG. Instead, these flexible or bent structures lead to the capture of a nearby site of damage that is more efficient than that of a continuous B-form duplex. The ability of AAG to negotiate these helix discontinuities is inconsistent with a sliding mode of diffusion but can be readily explained by a hopping mode that involves microscopic dissociation and reassociation. These experiments provide evidence of relatively long-range hops that allow a searching protein to navigate around DNA binding proteins that would serve as obstacles to a sliding protein.

  15. Structure and ionic diffusion of alkaline-earth ions in mixed cation glasses

    SciTech Connect

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

    2015-08-15

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

  16. Cation-Dependent Gold Recovery with α-Cyclodextrin Facilitated by Second-Sphere Coordination.

    PubMed

    Liu, Zhichang; Samanta, Avik; Lei, Juying; Sun, Junling; Wang, Yuping; Stoddart, J Fraser

    2016-09-14

    Herein, we report an alkali metal cation-dependent approach to gold recovery, facilitated by second-sphere coordination with eco-friendly α-cyclodextrin (α-CD). Upon mixing eight salts composed of Na(+), K(+), Rb(+), or Cs(+) cations and [AuX4](-) (X = Cl/Br) anions with α-, β-, or γ-CD in water, co-precipitates form selectively from the three (out of 24) aqueous solutions containing α-CD with KAuBr4, RbAuBr4, and CsAuBr4, from which the combination of α-CD and KAuBr4 affords the highest yield. Single-crystal X-ray analyses reveal that in 20 of the 24 adducts CD and [AuX4](-) anions form 2:1 sandwich-type second-sphere adducts driven partially by [C-H···X-Au] interactions between [AuX4](-) anions and the primary faces of two neighboring CDs. In the adduct formed between α-CD and KAuBr4, a [K(OH2)6](+) cation is encapsulated inside the cavity between the secondary faces of two α-CDs, leading to highly efficient precipitation owing to the formation of a cation/anion alternating ion wire residing inside a continuous α-CD nanotube. By contrast, in the other 19 adducts, the cations are coordinated by OH groups and glucopyranosyl ring O atoms in CDs. The strong coordination of Rb(+) and Cs(+) cations by these ligands, in conjunction with the stereoelectronically favorable binding of [AuBr4](-) anions with two α-CDs, facilitates the co-precipitation of the two adducts formed between α-CD with RbAuBr4 and CsAuBr4. In order to develop an efficient process for green gold recovery, the co-precipitation yield of α-CD and KAuBr4 has been optimized regarding both the temperature and the molar ratio of α-CD to KAuBr4. PMID:27518451

  17. Facilitated diffusion framework for transcription factor search with conformational changes

    NASA Astrophysics Data System (ADS)

    Cartailler, Jérôme; Reingruber, Jürgen

    2015-07-01

    Cellular responses often require the fast activation or repression of specific genes, which depends on transcription factors (TFs) that have to quickly find the promoters of these genes within a large genome. TFs search for their DNA promoter target by alternating between bulk diffusion and sliding along the DNA, a mechanism known as facilitated diffusion. We study a facilitated diffusion framework with switching between three search modes: a bulk mode and two sliding modes triggered by conformational changes between two protein conformations. In one conformation (search mode) the TF interacts unspecifically with the DNA backbone resulting in fast sliding. In the other conformation (recognition mode) it interacts specifically and strongly with DNA base pairs leading to slow displacement. From the bulk, a TF associates with the DNA at a random position that is correlated with the previous dissociation point, which implicitly is a function of the DNA structure. The target affinity depends on the conformation. We derive exact expressions for the mean first passage time (MFPT) to bind to the promoter and the conditional probability to bind before detaching when arriving at the promoter site. We systematically explore the parameter space and compare various search scenarios. We compare our results with experimental data for the dimeric Lac repressor search in E. coli bacteria. We find that a coiled DNA conformation is absolutely necessary for a fast MFPT. With frequent spontaneous conformational changes, a fast search time is achieved even when a TF becomes immobilized in the recognition state due to the specific bindings. We find a MFPT compatible with experimental data in presence of a specific TF-DNA interaction energy that has a Gaussian distribution with a large variance.

  18. 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.

  19. Diffusion of cations in chromia layers grown on iron-base alloys

    SciTech Connect

    Lobnig, R.E.; Hennesen, K.; Grabke, H.J. ); Schmidt, H.P.

    1992-02-01

    Diffusion of the cations Cr, Fe, Mn, and Ni in Cr{sub 2}O{sub 3} has been investigated at 1,173 K. The diffusion measurements were performed on chromia layers grown on the model alloys Fe-20Cr and Fe-20Cr-12Ni in order to consider effects of small amounts of dissolved alien cations in Cr{sub 2}O{sub 3}. The samples were diffusion annealed in H{sub 2}-H{sub 2}O at an oxygen partial pressure close to the Cr{sub 2}O{sub 3}/Cr equilibrium. For all tracers the lattice-diffusion coefficients are 3-5 orders of magnitude smaller than the grain-boundary diffusion coefficients. The lattice diffusivity of Mn is about two orders of magnitude greater than the other lattice-diffusion coefficients, especially in Cr{sub 2}O{sub 3} grown on Fe-20Cr-12Ni. The values of the diffusion coefficients for Cr, Fe, and Ni are in the same range. Diffusion of the tracers in Cr{sub 2}O{sub 3} grown on different alloys did not show significant differences with the exception of Mn.

  20. The mathematical model of dye diffusion and adsorption on modified cellulose with triazine derivatives containing cationic and anionic groups

    NASA Astrophysics Data System (ADS)

    Xie, K.; Hou, A.; Chen, Y.

    2008-02-01

    Cellulose fabric is chemically modified with the compounds containing cationic and anionic groups. The molecular chains of modified cellulose have both cationic and anionic groups. Dye diffusion properties on modified cellulose are discussed. The dye adsorption and diffusion on modified cellulose are higher than those on unmodified cellulose. The diffusion properties of dyes at different temperature are discussed. Compared with unmodified cellulose, the diffusion processing of dyes in the modified cotton cellulose shows significant change.

  1. Colloid-Facilitated Transport of Cations in an Unsaturated Fractured Soil Under Transient Conditions

    SciTech Connect

    Ryan, Joseph

    2015-01-31

    Rainfall experiments were conducted using intact soil cores and an instrumented soil pedon to examine the effect of physical heterogeneity and rainfall characteristics on the mobilization of colloids, organic matter, cesium, and strontium in a fractured soil. To measure the spatial variability of infiltration of colloids and contaminants, samples were collected through a 19-port grid placed below the soil core in laboratory study and in 27 samplers at multiple depths in the soil pedon in the field study. Cesium and strontium were applied to the soil cores and the soil pedon prior to mobilization experiments. Rainwater solutions of multiple ionic strengths and organic matter concentrations were applied to the soil cores and soil pedon to mobilize in situ colloids, cesium, and strontium. The mobilization of colloids and metal cations occurred through preferential flow paths in the soil cores. Compared to steady rainfall, greater amounts of colloids were mobilized during rainfall interrupted by pauses, which indicates that the supply of colloids to be mobilized was replenished during the pauses. A maximum in the amount of mobilized colloids were mobilized during a rainfall following a pause of 2.5 d. Pauses of shorter or longer duration resulted in less colloid mobilization. Freeze-thaw cycles, a transient condition in winter, enhanced colloid mobilization and colloid-facilitated transport of cesium and strontium in the soil cores. The exchange of solutes between the soil matrix and macropores caused a hysteretic mobilization of colloids, cesium, and strontium during changes in ionic strength. Colloid-facilitated mobilization of cesium and strontium was important at low ionic strength in fractures where slow flow allowed greater exchange of flow between the fractures and the surrounding matrix. The release of cesium and strontium by cation exchange occurred at high ionic strength in fractures where there is a little exchange of pore water with the surrounding matrix

  2. Enhancement of cation diffusion rates across the 410-kilometer discontinuity in Earth's mantle

    PubMed

    Chakraborty; Knoche; Schulze; Rubie; Dobson; Ross; Angel

    1999-01-15

    Rates of cation diffusion (magnesium, iron, and nickel) have been determined in olivine and its high-pressure polymorph, wadsleyite, at 9 to 15 gigapascals and 1100 degrees to 1400 degreesC for compositions that are relevant to Earth's mantle. Diffusion in olivine becomes strongly dependent on composition at high pressure. In wadsleyite, diffusion is one to two orders of magnitude faster than in olivine, depending on temperature. Homogenization of mantle heterogeneities (chemical mixing) and mineral transformations involving a magnesium-iron exchange will therefore occur considerably faster in the transition zone than at depths of less than 410 kilometers. PMID:9888846

  3. Modeling cation diffusion in compacted water-saturatedNa-bentonite at low ionic strength

    SciTech Connect

    Bourg, Ian C.; Sposito, Garrison; Bourg, Alain C.M.

    2007-08-28

    Sodium bentonites are used as barrier materials for the isolation of landfills and are under consideration for a similar use in the subsurface storage of high-level radioactive waste. The performance of these barriers is determined in large part by molecular diffusion in the bentonite pore space. We tested two current models of cation diffusion in bentonite against experimental data on the relative apparent diffusion coefficients of two representative cations, sodium and strontium. On the 'macropore/nanopore' model, solute molecules are divided into two categories, with unequal pore-scale diffusion coefficients, based on location: in macropores or in interlayer nanopores. On the 'surface diffusion' model, solute molecules are divided into categories based on chemical speciation: dissolved or adsorbed. The macropore/nanopore model agrees with all experimental data at partial montmorillonite dry densities ranging from 0.2 (a dilute bentonite gel) to 1.7 kg dm{sup -3} (a highly compacted bentonite with most of its pore space located in interlayer nanopores), whereas the surface diffusion model fails at partial montmorillonite dry densities greater than about 1.2 kg dm{sup -3}.

  4. Modeling cation diffusion in compacted water-saturated sodium bentonite at low ionic strength.

    PubMed

    Bourg, Ian C; Sposito, Garrison; Bourg, Alain C M

    2007-12-01

    Sodium bentonites are used as barrier materials for the isolation of landfills and are under consideration for a similar use in the subsurface storage of high-level radioactive waste. The performance of these barriers is determined in large part by molecular diffusion in the bentonite pore space. We tested two current models of cation diffusion in bentonite against experimental data on the relative apparent diffusion coefficients of two representative cations, sodium and strontium. On the "macropore/nanopore" model, solute molecules are divided into two categories, with unequal pore-scale diffusion coefficients, based on location: in macropores or in interlayer nanopores. On the "surface diffusion" model, solute molecules are divided into categories based on chemical speciation: dissolved or adsorbed. The macropore/nanopore model agrees with all experimental data at partial montmorillonite dry densities ranging from 0.2 (a dilute bentonite gel) to 1.7 kg dm(-3) (a highly compacted bentonite with most of its pore space located in interlayer nanopores), whereas the surface diffusion model fails at partial montmorillonite dry densities greater than about 1.3 kg dm(-3). PMID:18186346

  5. Do epidermal lens cells facilitate the absorptance of diffuse light?

    PubMed

    Brodersen, Craig R; Vogelmann, Thomas C

    2007-07-01

    Many understory plants rely on diffuse light for photosynthesis because direct light is usually scattered by upper canopy layers before it strikes the forest floor. There is a considerable gap in the literature concerning the interaction of direct and diffuse light with leaves. Some understory plants have well-developed lens-shaped epidermal cells, which have long been thought to increase the absorption of diffuse light. To assess the role of epidermal cell shape in capturing direct vs. diffuse light, we measured leaf reflectance and transmittance with an integrating sphere system using leaves with flat (Begonia erythrophylla, Citrus reticulata, and Ficus benjamina) and lens-shaped epidermal cells (B. bowerae, Colocasia esculenta, and Impatiens velvetea). In all species examined, more light was absorbed when leaves were irradiated with direct as opposed to diffuse light. When leaves were irradiated with diffuse light, more light was transmitted and more was reflected in both leaf types, resulting in absorptance values 2-3% lower than in leaves irradiated with direct light. These data suggest that lens-shaped epidermal cells do not aid the capture of diffuse light. Palisade and mesophyll cell anatomy and leaf thickness appear to have more influence in the capture and absorption of light than does epidermal cell shape.

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

    DOE PAGES

    Uberuaga, Blas Pedro; Pilania, Ghanshyam

    2015-07-08

    Perovskite structured oxides (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

  7. 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.

  8. Instantaneous normal mode prediction for cation and anion diffusion in ionic melts

    NASA Astrophysics Data System (ADS)

    Ribeiro, M. C. C.; Madden, P. A.

    1997-05-01

    Instantaneous normal mode (INM) analysis was undertaken for several ionic melts: NaCl at six distinct thermodynamic states, and for a particular state of liquid LiCl, LiF, KF, KI, NaI, ZnCl2, and CuCl. In this Communication, we show that, in most cases, the ratio between the diffusion constants for cations (Dca) and anions (Dan) is predicted from the average frequency of the real ("stable" <ωs>) and imaginary ("unstable" <ωu>) frequency modes of the projection of the total density of states on cations and anions, respectively. The proposed relationship, Dca/Dan=(mca-1<ωu>ca<ωs>ca-2)ṡ(man-1<ωu>an<ωs>an-2)-1, where mi is the mass of a particular species, is suggested by Keyes' INM theory for diffusion [J. Chem. Phys. 101, 5081 (1994)], with the further assumption that the parameters which are related to the topology of the multidimensional potential surface are equal for cations and anions. The above equation is shown to be valid for the simple melts NaCl, LiCl, LiF, KF, KI, and NaI, but to fail for the network forming melt ZnCl2 and for CuCl, which shows fast ionic diffusion characteristics.

  9. Impact of network topology on cationic diffusion and hardness of borate glass surfaces

    NASA Astrophysics Data System (ADS)

    Smedskjaer, Morten M.; Mauro, John C.; Sen, Sabyasachi; Deubener, Joachim; Yue, Yuanzheng

    2010-10-01

    The connection between bulk glass properties and network topology is now well established. However, there has been little attention paid to the impact of network topology on the surface properties of glass. In this work, we report the impact of the network topology on both the transport properties (such as cationic inward diffusion) and the mechanical properties (such as hardness) of borate glasses with modified surfaces. We choose soda lime borate systems as the object of this study because of their interesting topological features, e.g., boron anomaly. An inward diffusion mechanism is employed to modify the glass surface compositions and hence the surface topology. We show that accurate quantitative predictions of the hardness of the modified surfaces can be made using topological constraint theory with temperature-dependent constraints. Experimental results reveal that Ca2+ diffusion is most intense in glasses with lowest BO4 fraction, whereas Na+ diffusion is only significant when nonbridging oxygens start to form. These phenomena are interpreted in terms of the atomic packing and the local electrostatic environments of the cations.

  10. Effect of cation on diffusion coefficient of ionic liquids at onion-like carbon electrodes.

    PubMed

    Van Aken, Katherine L; McDonough, John K; Li, Song; Feng, Guang; Chathoth, Suresh M; Mamontov, Eugene; Fulvio, Pasquale F; Cummings, Peter T; Dai, Sheng; Gogotsi, Yury

    2014-07-16

    While most supercapacitors are limited in their performance by the stability of the electrolyte, using neat ionic liquids (ILs) as the electrolyte can expand the voltage window and temperature range of operation. In this study, ILs with bis(trifluoromethylsulfonyl)imide (Tf2N) as the anion were investigated as the electrolyte in onion-like carbon-based electrochemical capacitors. To probe the influence of cations on the electrochemical performance of supercapacitors, three different cations were used: 1-ethyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium and 1,6-bis(3-methylimidazolium-1-yl). A series of electrochemical characterization tests was performed using cyclic voltammetry (CV), galvanostatic cycling and electrochemical impedance spectroscopy (EIS). Diffusion coefficients were measured using EIS and correlated with quasielastic neutron scattering and molecular dynamics simulation. These three techniques were used in parallel to confirm a consistent trend between the three ILs. It was found that the IL with the smaller sized cation had a larger diffusion coefficient, leading to a higher capacitance at faster charge-discharge rates. Furthermore, the IL electrolyte performance was correlated with increasing temperature, which limited the voltage stability window and led to the formation of a solid electrolyte interphase on the carbon electrode surface, evident in both the CV and EIS experiments.

  11. Gel for Simultaneous Chemical Imaging of Anionic and Cationic Solutes Using Diffusive Gradients in Thin Films

    PubMed Central

    2013-01-01

    We report on a novel gel based on diffusive gradients in thin films (DGT) for the simultaneous measurement of cations and anions and its suitability for high resolution chemical imaging by using laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). The new high resolution mixed binding gel (HR-MBG) is based on zirconium-hydroxide and suspended particulate reagent-iminodiacetate (SPR-IDA) as resin materials which are embedded in an ether-based urethane polymer hydrogel. The use of this polymer hydrogel material allows the production of ultrathin, highly stable and tear-proof resin gel layers with superior handling properties compared to existing ultrathin polyacrylamide gels. The gel was characterized regarding its uptake kinetics, the anion and cation capacities, and the effects of pH, ionic strength, and aging on the performance of the HR-MBG. Our results demonstrate the capability of this novel gel for concomitant sampling of anions and cations. The suitability of this new gel type for DGT chemical imaging at submm spatial resolution in soils using LA-ICPMS is shown. 2D images of P, As, Co, Cu, Mn, and Zn distributions around roots of Zea mays L. demonstrate the new opportunities offered by the HR-MBG for high-resolution mapping of solute dynamics in soil and sediment hotspots, such as the rhizosphere, by simultaneous observation of anionic and cationic solute species. PMID:24256092

  12. Gel for simultaneous chemical imaging of anionic and cationic solutes using diffusive gradients in thin films.

    PubMed

    Kreuzeder, Andreas; Santner, Jakob; Prohaska, Thomas; Wenzel, Walter W

    2013-12-17

    We report on a novel gel based on diffusive gradients in thin films (DGT) for the simultaneous measurement of cations and anions and its suitability for high resolution chemical imaging by using laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). The new high resolution mixed binding gel (HR-MBG) is based on zirconium-hydroxide and suspended particulate reagent-iminodiacetate (SPR-IDA) as resin materials which are embedded in an ether-based urethane polymer hydrogel. The use of this polymer hydrogel material allows the production of ultrathin, highly stable and tear-proof resin gel layers with superior handling properties compared to existing ultrathin polyacrylamide gels. The gel was characterized regarding its uptake kinetics, the anion and cation capacities, and the effects of pH, ionic strength, and aging on the performance of the HR-MBG. Our results demonstrate the capability of this novel gel for concomitant sampling of anions and cations. The suitability of this new gel type for DGT chemical imaging at submm spatial resolution in soils using LA-ICPMS is shown. 2D images of P, As, Co, Cu, Mn, and Zn distributions around roots of Zea mays L. demonstrate the new opportunities offered by the HR-MBG for high-resolution mapping of solute dynamics in soil and sediment hotspots, such as the rhizosphere, by simultaneous observation of anionic and cationic solute species.

  13. Gel for simultaneous chemical imaging of anionic and cationic solutes using diffusive gradients in thin films.

    PubMed

    Kreuzeder, Andreas; Santner, Jakob; Prohaska, Thomas; Wenzel, Walter W

    2013-12-17

    We report on a novel gel based on diffusive gradients in thin films (DGT) for the simultaneous measurement of cations and anions and its suitability for high resolution chemical imaging by using laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). The new high resolution mixed binding gel (HR-MBG) is based on zirconium-hydroxide and suspended particulate reagent-iminodiacetate (SPR-IDA) as resin materials which are embedded in an ether-based urethane polymer hydrogel. The use of this polymer hydrogel material allows the production of ultrathin, highly stable and tear-proof resin gel layers with superior handling properties compared to existing ultrathin polyacrylamide gels. The gel was characterized regarding its uptake kinetics, the anion and cation capacities, and the effects of pH, ionic strength, and aging on the performance of the HR-MBG. Our results demonstrate the capability of this novel gel for concomitant sampling of anions and cations. The suitability of this new gel type for DGT chemical imaging at submm spatial resolution in soils using LA-ICPMS is shown. 2D images of P, As, Co, Cu, Mn, and Zn distributions around roots of Zea mays L. demonstrate the new opportunities offered by the HR-MBG for high-resolution mapping of solute dynamics in soil and sediment hotspots, such as the rhizosphere, by simultaneous observation of anionic and cationic solute species. PMID:24256092

  14. Specific aquaporins facilitate the diffusion of hydrogen peroxide across membranes.

    PubMed

    Bienert, Gerd P; Møller, Anders L B; Kristiansen, Kim A; Schulz, Alexander; Møller, Ian M; Schjoerring, Jan K; Jahn, Thomas P

    2007-01-12

    The metabolism of aerobic organisms continuously produces reactive oxygen species. Although potentially toxic, these compounds also function in signaling. One important feature of signaling compounds is their ability to move between different compartments, e.g. to cross membranes. Here we present evidence that aquaporins can channel hydrogen peroxide (H2O2). Twenty-four aquaporins from plants and mammals were screened in five yeast strains differing in sensitivity toward oxidative stress. Expression of human AQP8 and plant Arabidopsis TIP1;1 and TIP1;2 in yeast decreased growth and survival in the presence of H2O2. Further evidence for aquaporin-mediated H2O2 diffusion was obtained by a fluorescence assay with intact yeast cells using an intracellular reactive oxygen species-sensitive fluorescent dye. Application of silver ions (Ag+), which block aquaporin-mediated water diffusion in a fast kinetics swelling assay, also reversed both the aquaporin-dependent growth repression and the H2O2-induced fluorescence. Our results present the first molecular genetic evidence for the diffusion of H2O2 through specific members of the aquaporin family.

  15. Cation Diffusivity and the Mixed Network Former Effect in Borosilicate Glasses.

    PubMed

    Smedskjaer, Morten M; Mauro, John C; Yue, Yuanzheng

    2015-06-11

    Understanding the structural origins of cationic diffusion processes in silicate glasses is important for high-tech applications of silicate glasses. For glasses with more than one network former, transport properties such as diffusivity are often nonlinear functions of the particular distribution of these network formers, a phenomenon known as the mixed network former effect. Here, we investigate the sodium-potassium interdiffusion (D̅Na-K) and the calcium inward diffusion (DCa) in soda lime borosilicate glasses with varying silica/borate ratio but constant modifier content. Indeed, the structural organization of borosilicate glasses results in a pronounced nonlinear composition dependence of D̅Na-K and DCa (i.e., the mixed network former effect). Initial addition of B2O3 to the glass system results in a significant decrease in both diffusivities, whereas the change in diffusivity per mole of added B2O3 decreases with increasing B2O3 concentration. Besides the influences of water content and atomic packing degree, we find that 99% of the composition dependence of log D̅Na-K can be ascribed to the change in concentration of tetrahedral boron groups. This indicates that the formation of BO4/2 groups slows down diffusion processes of alkali and alkaline earth ions. Therefore, the mixed network former effect of the studied glass series is linked with the change of the concentration of tetrahedral boron groups, which is caused by the interactions between the different types of network formers.

  16. EVIDENCE FOR DIACETYLENE CATION AS THE CARRIER OF A DIFFUSE INTERSTELLAR BAND

    SciTech Connect

    Krelowski, J.; Beletsky, Y.; LoCurto, G.; Galazutdinov, G. A.; Kolos, R.; Gronowski, M. E-mail: ybialets@eso.org E-mail: runizag@gmail.com

    2010-05-01

    High-quality spectra acquired at three different observatories point to the presence of a new diffuse interstellar band (DIB) at 5069 A. The spectral profile of this DIB matches published laboratory measurements of the diacetylene cation A {sup 2}{pi} {sub u} -X {sup 2}{pi} {sub g} (0-0) low-temperature gas-phase optical absorption. HC{sub 4}H{sup +} is approximately 60-80 times less abundant than CH along the analyzed lines of sight. Only an upper limit could presently be inferred from the search for an analogous band of the triacetylene cation HC{sub 6}H{sup +}, expected at 6001.1 A, which implies the HC{sub 6}H{sup +} to HC{sub 4}H{sup +} ratio of less than {approx}1/3.

  17. The rate of the deoxygenation reaction limits myoglobin- and hemoglobin-facilitated O₂ diffusion in cells.

    PubMed

    Endeward, Volker

    2012-05-01

    A mathematical model describing facilitation of O(2) diffusion by the diffusion of myoglobin and hemoglobin is presented. The equations are solved numerically by a finite-difference method for the conditions as they prevail in cardiac and skeletal muscle and in red cells without major simplifications. It is demonstrated that, in the range of intracellular diffusion distances, the degree of facilitation is limited by the rate of the chemical reaction between myglobin or hemoglobin and O(2). The results are presented in the form of relationships between the degree of facilitation and the length of the diffusion path on the basis of the known kinetics of the oxygenation-deoxygenation reactions. It is concluded that the limitation by reaction kinetics reduces the maximally possible facilitated oxygen diffusion in cardiomyoctes by ∼50% and in skeletal muscle fibers by ∼ 20%. For human red blood cells, a reduction of facilitated O(2) diffusion by 36% is obtained in agreement with previous reports. This indicates that, especially in cardiomyocytes and red cells, chemical equilibrium between myoglobin or hemoglobin and O(2) is far from being established, an assumption that previously has often been made. Although the "O(2) transport function" of myoglobin in cardiac muscle cells thus is severely limited by the chemical reaction kinetics, and to a lesser extent also in skeletal muscle, it is noteworthy that the speed of release of O(2) from MbO(2), the "storage function," is not limited by the reaction kinetics under physiological conditions.

  18. The self-diffusion of water and saturated aliphatic alcohols in cation-exchange membranes

    NASA Astrophysics Data System (ADS)

    Volkov, V. I.; Kotov, V. V.; Netesova, G. A.

    2008-07-01

    The self-diffusion of water, methanol, ethanol, isopropanol, and butanol in membranes based on polyethylene and sulfonated copolymer of styrene and divinylbenzene (MK-100) and membranes based on sulfo-containing aromatic polyamides (PA) and a copolymer of 1,2,4,5-benzenetetracarboxylic acid with 4,4'-diaminodiphenyl oxide (PAK) was investigated by the pulsed magnetic field gradient NMR technique. In MK-100 sulfo cation-exchange membranes and PAK carboxylic membranes, two types of sorbate molecules with translational mobilities differing by an order of magnitude were observed. It was established that, in these membranes, the major diffusant portion was transferred trough transport channels formed by functional groups of membranes, counterions, and diffusant molecules (ionogenic channels). The conclusion was drawn that, in PA membranes, water and alcohol molecules were distributed uniformly and carbonyl croups of the polymeric matrix participated in the formation of transport channels. Relations between the structure of membranes, the character of diffusant-polymeric matrix interaction, and the translational mobility of sorbate molecules were found.

  19. Hydrogels facilitated by monovalent cations and their use as efficient dye adsorbents.

    PubMed

    Wang, Haiqiao; Xu, Wenlong; Song, Shasha; Feng, Lei; Song, Aixin; Hao, Jingcheng

    2014-05-01

    Gelation behavior of lithocholate (LC(-)) mixed with different monovalent cations in water was detected. The hydrogels consisting of tubular networks were formed by introducing alkali metal ions and NH4(+) to lithocholate aqueous solutions at room temperature. The formation of tubular structures was considered to be mainly driven by the electrostatic interaction with the assistance of a delicate balance of multiple noncovalent interactions. It is interesting that the increase in temperature can induce a significant enhancement in strength of the hydrogels, accompanied by the formation of bundles of tubules and larger size aggregates. The mechanism of the temperature-induced transition can be explained by the "salting-out" effect and the electric double layer model. The hydrogels showed very high adsorption efficiency and adsorption capability for the cationic dyes and were promising to act as toxic substance adsorbents.

  20. Bidirectional diffusion of ammonium and sodium cations in forward osmosis: role of membrane active layer surface chemistry and charge.

    PubMed

    Lu, Xinglin; Boo, Chanhee; Ma, Jun; Elimelech, Menachem

    2014-12-16

    Systematic fundamental understanding of mass transport in osmosis-driven membrane processes is important for further development of this emerging technology. In this work, we investigate the role of membrane surface chemistry and charge on bidirectional solute diffusion in forward osmosis (FO). In particular, bidirectional diffusion of ammonium (NH4(+)) and sodium (Na(+)) is examined using FO membranes with different materials and surface charge characteristics. Using an ammonium bicarbonate (NH4HCO3) draw solution, we observe dramatically enhanced cation fluxes with sodium chloride feed solution compared to that with deionized water feed solution for thin-film composite (TFC) FO membrane. However, the bidirectional diffusion of cations does not change, regardless of the type of feed solution, for cellulose triacetate (CTA) FO membrane. We relate this phenomenon to the membrane fixed surface charge by employing different feed solution pH to foster different protonation conditions for the carboxyl groups on the TFC membrane surface. Membrane surface modification is also carried out with the TFC membrane using ethylenediamine to alter carboxyl groups into amine groups. The modified TFC membrane, with less negatively charged groups, exhibits a significant decrease in the bidirectional diffusion of cations under the same conditions employed with the pristine TFC membrane. Based on our experimental observations, we propose Donnan dialysis as a mechanism responsible for enhanced bidirectional diffusion of cations in TFC membranes.

  1. Bidirectional diffusion of ammonium and sodium cations in forward osmosis: role of membrane active layer surface chemistry and charge.

    PubMed

    Lu, Xinglin; Boo, Chanhee; Ma, Jun; Elimelech, Menachem

    2014-12-16

    Systematic fundamental understanding of mass transport in osmosis-driven membrane processes is important for further development of this emerging technology. In this work, we investigate the role of membrane surface chemistry and charge on bidirectional solute diffusion in forward osmosis (FO). In particular, bidirectional diffusion of ammonium (NH4(+)) and sodium (Na(+)) is examined using FO membranes with different materials and surface charge characteristics. Using an ammonium bicarbonate (NH4HCO3) draw solution, we observe dramatically enhanced cation fluxes with sodium chloride feed solution compared to that with deionized water feed solution for thin-film composite (TFC) FO membrane. However, the bidirectional diffusion of cations does not change, regardless of the type of feed solution, for cellulose triacetate (CTA) FO membrane. We relate this phenomenon to the membrane fixed surface charge by employing different feed solution pH to foster different protonation conditions for the carboxyl groups on the TFC membrane surface. Membrane surface modification is also carried out with the TFC membrane using ethylenediamine to alter carboxyl groups into amine groups. The modified TFC membrane, with less negatively charged groups, exhibits a significant decrease in the bidirectional diffusion of cations under the same conditions employed with the pristine TFC membrane. Based on our experimental observations, we propose Donnan dialysis as a mechanism responsible for enhanced bidirectional diffusion of cations in TFC membranes. PMID:25418020

  2. The effect of the cation alkyl chain length on density and diffusion in dialkylpyrrolidinium bis(mandelato)borate ionic liquids.

    PubMed

    Filippov, Andrei; Taher, Mamoun; Shah, Faiz Ullah; Glavatskih, Sergei; Antzutkin, Oleg N

    2014-12-28

    The physicochemical properties of ionic liquids are strongly affected by the selective combination of the cations and anions comprising the ionic liquid. In particular, the length of the alkyl chains of ions has a clear influence on the ionic liquid's performance. In this paper, we study the self-diffusion of ions in a series of halogen-free boron-based ionic liquids (hf-BILs) containing bis(mandelato)borate anions and dialkylpyrrolidinium cations with long alkyl chains CnH2n+1 with n from 4 to 14 within a temperature range of 293-373 K. It was found that the hf-BILs with n = 4-7 have very similar diffusion coefficients, while hf-BILs with n = 10-14 exhibit two liquid sub-phases in almost the entire temperature range studied (293-353 K). Both liquid sub-phases differ in their diffusion coefficients, while values of the slower diffusion coefficients are close to those of hf-BILs with shorter alkyl chains. To explain the particular dependence of diffusion on the alkyl chain length, we examined the densities of the hf-BILs studied here. It was shown that the dependence of the density on the number of CH2 groups in long alkyl chains of cations can be accurately described using a "mosaic type" model, where regions of long alkyl chains of cations (named 'aliphatic' regions) and the residual chemical moieties in both cations and anions (named 'ionic' regions) give additive contributions. Changes in density due to an increase in temperature and the number of CH2 groups in the long alkyl chains of cations are determined predominantly by changes in the free volume of the 'ionic' regions, while 'aliphatic' regions are already highly compressed by van der Waals forces, which results in only infinitesimal changes in their free volumes with temperature.

  3. Effect of exchangeable cations on apparent diffusion of Ca 2+ ions in Na- and Ca-montmorillonite mixtures

    NASA Astrophysics Data System (ADS)

    Kozaki, T.; Sawaguchi, T.; Fujishima, A.; Sato, S.

    Compacted Na-bentonite, of which the major mineral is montmorillonite, is a candidate buffer material for the geological disposal of high-level radioactive waste. A potential alteration of the bentonite in a repository is the partial replacement of the exchangeable cations of Na + with Ca 2+. The Ca 2+ cations could be released from cementitious materials and diffuse into the buffer material in the repository. In this study, to evaluate the alteration that could reduce the performance of the bentonite buffer, the apparent diffusion coefficients of HTO and Ca 2+ ions were determined from non-steady, one-dimensional diffusion experiments using Na- and Ca-montmorillonite mixtures with different ionic equivalent fractions of Ca 2+ ions. The apparent diffusion coefficient of HTO at a dry density of 1.0 Mg m -3 slightly increased with an increase in the ionic equivalent fraction of Ca 2+ ions. However, the apparent diffusion coefficient of Ca 2+ and the activation energy for diffusion at the same dry density were independent of the ionic equivalent fraction of Ca 2+ ions. These findings suggest that unlike HTO, which can be postulated to diffuse mainly in pore water, Ca 2+ ion diffusion could occur predominantly in interlayer spaces, of which the basal spacing was determined to be constant by the XRD technique.

  4. A Model Based on Facilitated Passive Diffusion is Needed to Describe Root Water Entry through Aquaporins.

    PubMed

    Beaudette, Pc; Salon, C; Emery, Rjn

    2007-09-01

    Despite abundant evidence that water transfer from soil to xylem occurs along a pathway regulated by aquaporins (AQPs) water entry is still modeled using principles of ordinary passive diffusion. Problems with this model have been known for some time and include variable intrinsic properties of conductivity Lp, changing reflection coefficients, sigma, and an inability to accurately resolve osmotic differentials between the soil and xylem. Here we propose a model of water entry based on principles of facilitated passive diffusion and following Michaelis-Menten formalism. If one accepts that water entry is controlled, at least in part, by AQPs, then a model of ordinary passive diffusion is precluded, as it does not allow for facilitation kinetics. By contrast, recognition of facilitated water entry through protein channels could explain shortcomings of ordinary passive diffusion, such as diurnal variability in conductivity which we have recently shown is directly correlated to diurnal changes in PsPIP2-1 mRNA levels in Pisum sativum.

  5. Modeling sorption of divalent metal cations on hydrous manganese oxide using the diffuse double layer model

    USGS Publications Warehouse

    Tonkin, J.W.; Balistrieri, L.S.; Murray, J.W.

    2004-01-01

    Manganese oxides are important scavengers of trace metals and other contaminants in the environment. The inclusion of Mn oxides in predictive models, however, has been difficult due to the lack of a comprehensive set of sorption reactions consistent with a given surface complexation model (SCM), and the discrepancies between published sorption data and predictions using the available models. The authors have compiled a set of surface complexation reactions for synthetic hydrous Mn oxide (HMO) using a two surface site model and the diffuse double layer SCM which complements databases developed for hydrous Fe (III) oxide, goethite and crystalline Al oxide. This compilation encompasses a range of data observed in the literature for the complex HMO surface and provides an error envelope for predictions not well defined by fitting parameters for single or limited data sets. Data describing surface characteristics and cation sorption were compiled from the literature for the synthetic HMO phases birnessite, vernadite and ??-MnO2. A specific surface area of 746 m2g-1 and a surface site density of 2.1 mmol g-1 were determined from crystallographic data and considered fixed parameters in the model. Potentiometric titration data sets were adjusted to a pH1EP value of 2.2. Two site types (???XOH and ???YOH) were used. The fraction of total sites attributed to ???XOH (??) and pKa2 were optimized for each of 7 published potentiometric titration data sets using the computer program FITEQL3.2. pKa2 values of 2.35??0.077 (???XOH) and 6.06??0.040 (???YOH) were determined at the 95% confidence level. The calculated average ?? value was 0.64, with high and low values ranging from 1.0 to 0.24, respectively. pKa2 and ?? values and published cation sorption data were used subsequently to determine equilibrium surface complexation constants for Ba2+, Ca2+, Cd 2+, Co2+, Cu2+, Mg2+, Mn 2+, Ni2+, Pb2+, Sr2+ and Zn 2+. In addition, average model parameters were used to predict additional

  6. Substrate recognition by gelatinase A: the C-terminal domain facilitates surface diffusion.

    PubMed Central

    Collier, I E; Saffarian, S; Marmer, B L; Elson, E L; Goldberg, G

    2001-01-01

    An investigation of gelatinase A binding to gelatin produced results that are inconsistent with a traditional bimolecular Michaelis-Menten formalism but are effectively accounted for by a power law characteristic of fractal kinetics. The main reason for this inconsistency is that the bulk of the gelatinase A binding depends on its ability to diffuse laterally on the gelatin surface. Most interestingly, we show that the anomalous lateral diffusion and, consequently, the binding to gelatin is greatly facilitated by the C-terminal hemopexin-like domain of the enzyme whereas the specificity of binding resides with the fibronectin-like gelatin-binding domain. PMID:11566806

  7. A metal-ion NMR investigation of the antibiotic facilitated transport of monovalent cations through the walls of phospholipid vesicles. II. Sulfur-33 NMR

    SciTech Connect

    Buster, D.C.

    1988-01-01

    A technique has been developed to investigate the antibiotic facilitated transmembrane transport of monovalent cations using {sup 23}Na and {sup 7}Li Nuclear Magnetic Resonance spectroscopy. The initial portion of this thesis outlines the production and characterization of a model lipid system amenable to the NMR detection of cation transport. Large unilamellar vesicles (LUV) have been prepared from a 4:1 mixture of phosphatidylcholine and phosphatidylglycerol. The presence of the anionic chemical shift reagent dysprosium (III) tripolyphosphate, either inside or outside of the vesicles, allows for the spectroscopic separation of the NMR resonances arising from the inter- and extravesicular cation pools. The cation transporting properties of the channel-forming pentadecapeptide, gramicidin D, have been studied using the NMR technique.

  8. Time Dependent Density Functional Theory Calculations of Large Compact PAH Cations: Implications for the Diffuse Interstellar Bands

    NASA Technical Reports Server (NTRS)

    Weisman, Jennifer L.; Lee, Timothy J.; Salama, Farid; Gordon-Head, Martin; Kwak, Dochan (Technical Monitor)

    2002-01-01

    We investigate the electronic absorption spectra of several maximally pericondensed polycyclic aromatic hydrocarbon radical cations with time dependent density functional theory calculations. We find interesting trends in the vertical excitation energies and oscillator strengths for this series containing pyrene through circumcoronene, the largest species containing more than 50 carbon atoms. We discuss the implications of these new results for the size and structure distribution of the diffuse interstellar band carriers.

  9. Effects of diffusion of Co/Ni cations on sol-gel derived ZrO{sub 2} polymorphic transformations

    SciTech Connect

    Zeng, H.C.; Qian, M.

    1996-12-31

    Transition metal incorporated ZrO{sub 2} gel matrices have been prepared by impregnation method and investigated with FTIR/DTA/XRD. The metastable tetragonal-monoclinic-tetragonal-cubic phase transformations are revealed in the DTA heating process up to 1,400 C for the studied gels. High-temperature tetragonal to monoclinic transition is also observed in the cooling process. It is found that the diffusing metal cations stabilize the low-temperature tetragonal phase. However, for high-temperature (900 C) calcined gels, both as-prepared and metal-stabilized tetragonal phases are reduced substantially. Correlations between metal diffusion and gel polymorphic stabilities are also demonstrated.

  10. Matrix Diffusion and Colloid-Facilitated Transport in Fractured Rocks: Model and Parameter Validation

    SciTech Connect

    Zavarin, M

    2002-08-02

    In this report, we review the results of Reimus et al. (2000a; 2000b) regarding matrix diffusion and colloid-facilitated transport in fractured rock and evaluate the implications of these results on modeling fracture flow at the Nevada Test Site (NTS). In particular, we examine these data in the context of the recent Cheshire hydrologic source term (HST) model results (Pawloski et al., 2001). This report is divided into several sections. In the first, we evaluate the effective diffusion coefficient (D{sub e}) data reported in Reimus et al. (2000a) for conservative tracer species ({sup 3}H, {sup 14}C, and {sup 99}Tc) and fit a simple effective diffusion model to these data. In the second, we use the fitted effective diffusion model, in conjunction with a surface complexation model, to simulate plutonium-colloid transport and compare model results to data reported in Reimus et al. (2000b). In the third, we evaluate the implications of these data with regards to radionuclide transport through fractures at the field scale and, in particular, with regards to the Cheshire HST model (Pawloski et al., 2001). Finally, we make recommendations regarding future radionuclide transport modeling efforts at the NTS.

  11. Interaction between facilitated diffusion of glucose across the plasma membrane and its metabolism in Trichomonas vaginalis.

    PubMed

    ter Kuile, B H; Müller, M

    1993-06-01

    The parasitic protist Trichomonas vaginalis transports glucose across the plasma membrane by facilitated diffusion. The Km of the transporter for glucose was 1.6 mM. The uptake of labelled glucose in a minimal medium not allowing growth reached saturation only after 2.5 h, indicating the turnover of storage carbohydrate. Organisms grown on glucose showed higher activities both of the transporter and of the subsequent metabolic pathway than organisms grown on maltose. At low external glucose concentrations the transport step was rate limiting, at higher levels a subsequent enzymatic step. The uptake mechanism for glucose of T. vaginalis resembled that of parasitic kinetoplastid protists and Entamoeba histolytica.

  12. Diffusion in the system K2O-SrO-SiO2. II - Cation self-diffusion coefficients.

    NASA Technical Reports Server (NTRS)

    Varshneya, A. K.; Cooper, A. R.

    1972-01-01

    The self-diffusion coefficients were measured by introducing a slab of glass previously irradiated in a reactor between two slabs of unirradiated glass. By heating the specimens, etching them sequentially and determining the radioactivity, self-diffusion coefficients for K and Sr were measured. It is pointed out that the results obtained in the investigations appear to support the proposal that the network of the base glass predominantly controls the activation energy for the diffusion of ions.

  13. Facilitated diffusion of 6-deoxy-D-glucose in bakers' yeast: evidence against phosphorylation-associated transport of glucose.

    PubMed Central

    Romano, A H

    1982-01-01

    6-Deoxy-D-glucose, a structural homomorph of D-glucose which lacks a hydroxyl group at carbon 6 and thus cannot be phosphorylated, is transported by Saccharomyces cerevisiae via a facilitated diffusion system with affinity equivalent to that shown with D-glucose. This finding supports the facilitated diffusion mechanism for glucose transport and contradicts theories of transport-associated phosphorylation which hold that sugar phosphorylation is necessary for high-affinity operation of the glucose carrier. PMID:6754704

  14. Visual tracing of diffusion and biodistribution for amphiphilic cationic nanoparticles using photoacoustic imaging after ex vivo intravitreal injections

    PubMed Central

    Xu, Xu; Xu, Zhaokang; Liu, Junyi; Zhang, Zhaoliang; Chen, Hao; Li, Xingyi; Shi, Shuai

    2016-01-01

    To visually trace the diffusion and biodistribution of amphiphilic cation micelles after vitreous injection, various triblock copolymers of monomethoxy poly(ethylene glycol)–poly(ε-caprolactone)–polyethylenimine were synthesized with different structures of hydrophilic and hydrophobic segments, followed by labeling with near-infrared fluorescent dye Cyanine5 or Cyanine7. The micellar size, polydispersity index, and surface charge were measured by dynamic light scattering. The diffusion was monitored using photoacoustic imaging in real time after intravitreal injections. Moreover, the labeled nanoparticle distribution in the posterior segment of the eye was imaged histologically by confocal microscopy. The results showed that the hydrophilic segment increased vitreous diffusion, while a positive charge on the particle surface hindered diffusion. In addition, the particles diffused through the retinal layers and were enriched in the retinal pigment epithelial layer. This work tried to study the diffusion rate via a simple method by using visible images, and then provided basic data for the development of intraocular drug carriers. PMID:27785015

  15. Kinetics of self-assembly via facilitated diffusion: Formation of the transcription complex

    NASA Astrophysics Data System (ADS)

    Kalay, Ziya

    2015-10-01

    We present an analytically solvable model for self-assembly of a molecular complex on a filament. The process is driven by a seed molecule that undergoes facilitated diffusion, which is a search strategy that combines diffusion in three dimensions and one dimension. Our study is motivated by single-molecule-level observations revealing the dynamics of transcription factors that bind to the deoxyribonucleic acid at early stages of transcription. We calculate the probability that a complex made up of a given number of molecules is completely formed, as well as the distribution of completion times, upon the binding of a seed molecule at a target site on the filament (without explicitly modeling the three-dimensional diffusion that precedes binding). We compare two different mechanisms of assembly where molecules bind in sequential and random order. Our results indicate that while the probability of completion is greater for random binding, the completion time scales exponentially with the size of the complex; in contrast, it scales as a power law or slower for sequential binding, asymptotically. Furthermore, we provide model predictions for the dissociation and residence times of the seed molecule, which are observables accessible in single-molecule tracking experiments.

  16. Matrix diffusion of simple cations, anions, and neutral species in fractured crystalline rocks

    SciTech Connect

    Sato, Haruo . Tokai Works)

    1999-08-01

    The diffusion of radionuclides into the pore spaces of a rock matrix and the pore properties in fractured crystalline rocks were studied. The work concentrated on the predominant water-conducting fracture system in the host granodiorite of the Kamaishi In Situ Test Site, which consists of fracture fillings and altered grandodiorite. Through-diffusion experiments to obtain effective and apparent diffusion coefficients (De and Da, respectively) for Na[sup +], Cs[sup +], HTO, Cl[sup [minus

  17. Stomatal crypts may facilitate diffusion of CO(2) to adaxial mesophyll cells in thick sclerophylls.

    PubMed

    Hassiotou, Foteini; Evans, John R; Ludwig, Martha; Veneklaas, Erik J

    2009-11-01

    In some plants, stomata are exclusively located in epidermal depressions called crypts. It has been argued that crypts function to reduce transpiration; however, the occurrence of crypts in species from both arid and wet environments suggests that crypts may play another role. The genus Banksia was chosen to examine quantitative relationships between crypt morphology and leaf structural and physiological traits to gain insight into the functional significance of crypts. Crypt resistance to water vapour and CO(2) diffusion was calculated by treating crypts as an additional boundary layer partially covering one leaf surface. Gas exchange measurements of polypropylene meshes confirmed the validity of this approach. Stomatal resistance was calculated as leaf resistance minus calculated crypt resistance. Stomata contributed significantly more than crypts to leaf resistance. Crypt depth increased and accounted for an increasing proportion of leaf resistance in species with greater leaf thickness and leaf dry mass per area. All Banksia species examined with leaves thicker than 0.6 mm had their stomata in deep crypts. We propose that crypts function to facilitate CO(2) diffusion from the abaxial surface to adaxial palisade cells in thick leaves. This and other possible functions of stomatal crypts, including a role in water use, are discussed.

  18. Cation self-diffusion of 44Ca, 88Y, and 96Zr in single-crystalline calcia- and yttria-doped zirconia

    NASA Astrophysics Data System (ADS)

    Kilo, M.; Taylor, M. A.; Argirusis, Ch.; Borchardt, G.; Lesage, B.; Weber, S.; Scherrer, S.; Scherrer, H.; Schroeder, M.; Martin, M.

    2003-12-01

    Self-diffusion of calcium, yttrium, and zirconium in single-crystalline YSZ and CSZ (YSZ: yttria-stabilized zirconia; containing 10 to 32 mol % Y2O3; CSZ: calcia-stabilized zirconia; containing 11 and 17 mol % CaO) was measured at temperatures between 960 and 1700 °C. For zirconium and calcium diffusion, the stable isotopes 44Ca and 96Zr were used as tracers and the samples were analyzed with secondary ion mass spectrometry. In the case of yttrium diffusion, the radioactive tracer 88Y was used and an abrasive sectioning technique was applied. Zirconium bulk diffusion is slower than yttrium and calcium bulk diffusion, and there is a nearly linear correlation of diffusion coefficient with cation radius. In YSZ, zirconium and yttrium bulk diffusivity are maximum for a stabilizer content of 10-11 mol %, while in CSZ both calcium and zirconium tracer diffusion are independent of the calcium content. The activation enthalpy of yttrium stabilizer bulk diffusion (4.2 eV) is, as in CSZ, slightly smaller than for zirconium bulk diffusion (4.5 eV). The yttrium dislocation pipe diffusivity is five to six orders of magnitude faster than the bulk diffusivity, and its activation enthalpy (3.5 eV) is also smaller than that of the bulk diffusion. From the activation enthalpy and from the concentration dependence of the cation bulk diffusion, it is concluded that the cation diffusion occurs either via free vacancies (VZr4' in YSZ) or via bound vacancies ([VZr4'-2VO2•]x in CSZ).

  19. Tuning Equilibrium Compositions in Colloidal Cd1-xMnxSe Nanocrystals Using Diffusion Doping and Cation Exchange.

    PubMed

    Barrows, Charles J; Chakraborty, Pradip; Kornowske, Lindsey M; Gamelin, Daniel R

    2016-01-26

    The physical properties of semiconductor nanocrystals can be tuned dramatically via composition control. Here, we report a detailed investigation of the synthesis of high-quality colloidal Cd1-xMnxSe nanocrystals by diffusion doping of preformed CdSe nanocrystals. Until recently, Cd1-xMnxSe nanocrystals proved elusive because of kinetic incompatibilities between Mn(2+) and Cd(2+) chemistries. Diffusion doping allows Cd1-xMnxSe nanocrystals to be prepared under thermodynamic rather than kinetic control, allowing access to broader composition ranges. We now investigate this chemistry as a model system for understanding the characteristics of nanocrystal diffusion doping more deeply. From the present work, a Se(2-)-limited reaction regime is identified, in which Mn(2+) diffusion into CdSe nanocrystals is gated by added Se(2-), and equilibrium compositions are proportional to the amount of added Se(2-). At large added Se(2-) concentrations, a solubility-limited regime is also identified, in which x = xmax = ∼0.31, independent of the amount of added Se(2-). We further demonstrate that Mn(2+) in-diffusion can be reversed by cation exchange with Cd(2+) under exactly the same reaction conditions, purifying Cd1-xMnxSe nanocrystals back to CdSe nanocrystals with fine tunability. These chemistries offer exceptional composition control in Cd1-xMnxSe NCs, providing opportunities for fundamental studies of impurity diffusion in nanocrystals and for development of compositionally tuned nanocrystals with diverse applications ranging from solar energy conversion to spin-based photonics. PMID:26643033

  20. Effect of cation distribution on self-diffusion of molecular hydrogen in Na3Al3Si3O12 sodalite: a molecular dynamics study.

    PubMed

    van den Berg, A W C; Bromley, S T; Flikkema, E; Jansen, J C

    2004-11-22

    The diffusion of hydrogen in sodium aluminum sodalite (NaAlSi-SOD) is modeled using classical molecular dynamics, allowing for full flexibility of the host framework, in the temperature range 800-1200 K. From these simulations, the self-diffusion coefficient is determined as a function of temperature and the hydrogen uptake at low equilibrium hydrogen concentration is estimated at 573 K. The influence of the cation distribution over the framework on the hydrogen self-diffusion is investigated by comparing results employing a low energy fully ordered cation distribution with those obtained using a less ordered distribution. The cation distribution is found to have a surprisingly large influence on the diffusion, which appears to be due to the difference in framework flexibility for different cation distributions, the occurrence of correlated hopping in case of the ordered distribution, and the different nature of the diffusion processes in both systems. Compared to our previously reported calculations on all silica sodalite (all-Si-SOD), the hydrogen diffusion coefficient of sodium aluminum sodalite is higher in the case of the ordered distribution and lower in case of the disordered distribution. The hydrogen uptake rates of all-Si-SOD and NaSiAl-SOD are comparable at high temperatures (approximately 1000 K) and lower for all-Si-SOD at lower temperatures (approximately 400 K).

  1. How a protein searches for its site on DNA: the mechanism of facilitated diffusion

    NASA Astrophysics Data System (ADS)

    Mirny, Leonid; Slutsky, Michael; Wunderlich, Zeba; Tafvizi, Anahita; Leith, Jason; Kosmrlj, Andrej

    2009-10-01

    A number of vital biological processes rely on fast and precise recognition of a specific DNA sequence (site) by a protein. How can a protein find its site on a long DNA molecule among 106-109 decoy sites? Here, we present our recent studies of the protein-DNA search problem. Seminal biophysical works suggested that the protein-DNA search is facilitated by 1D diffusion of the protein along DNA (sliding). We present a simple framework to calculate the mean search time and focus on several new aspects of the process such as the roles of DNA sequence and protein conformational flexibility. We demonstrate that coupling of DNA recognition with conformational transition within the protein-DNA complex is essential for fast search. To approach the complexity of the in vivo environment, we examine how the search can proceed at realistic DNA concentrations and binding constants. We propose a new mechanism for local distance-dependent search that is likely essential in bacteria. Simulations of the search on tightly packed DNA and crowded DNA demonstrate that our theoretical framework can be extended to correctly predicts search time in such complicated environments. We relate our findings to a broad range of experiments and summarize the results of our recent single-molecule studies of a eukaryotic protein (p53) sliding along DNA.

  2. The effective charge number and diffusion coefficient of cationic cytochrome c in aqueous solution.

    PubMed

    Kontturi, A K; Kontturi, K; Niinikoski, P; Savonen, A; Vuoristo, M

    1992-04-01

    The diffusion coefficient and the effective charge number of cytochrome c as a function of ionic strength, temperature and pH have been measured. The measurements were carried out using a method based on a convective diffusion process across a porous membrane. The effect of ionic strength was studied in an NaCl solution the concentration of which varied from 0.001 to 1.0 M. The temperature range studied was 10-50 degrees C, and the pH values studied were 4.0, 6.5 and 8.25. The diffusion coefficient is fairly constant as a function of ionic strength and pH, and Walden's rule is valid in the temperature range studied. The effective charge number is practically constant (ca. 2) in the concentration range studied, except in 0.001 M solution, where it is the same as the titrated value. The charge number decreases slightly in the temperature range 10-30 degrees C, but seems to drop suddenly to zero at ca. 40 degrees C. Measurements using heavy water (D2O) as a solvent instead of water did not give zero charge at 40 degrees C for cytochrome c. PMID:1325179

  3. Channel-facilitated diffusion boosted by particle binding at the channel entrance.

    PubMed

    Pagliara, Stefano; Dettmer, Simon L; Keyser, Ulrich F

    2014-07-25

    We investigate single-file diffusion of Brownian particles in arrays of closely confining microchannels permeated by a variety of attractive optical potentials and connecting two baths with equal particle concentration. We simultaneously test free diffusion in the channel, diffusion in optical traps coupled in the center of the channel, and diffusion in traps extending into the baths. We found that both classes of attractive optical potentials enhance the translocation rate through the channel with respect to free diffusion. Surprisingly, for the latter class of potentials we measure a 40-fold enhancement in the translocation rate with respect to free diffusion and find a sublinear power law dependence of the translocation rate on the average number of particles in the channel. Our results reveal the function of particle binding at the channel entrances for diffusive transport and open the way to a better understanding of membrane transport and design of synthetic membranes with enhanced diffusion rate. PMID:25105657

  4. Channel-Facilitated Diffusion Boosted by Particle Binding at the Channel Entrance

    NASA Astrophysics Data System (ADS)

    Pagliara, Stefano; Dettmer, Simon L.; Keyser, Ulrich F.

    2014-07-01

    We investigate single-file diffusion of Brownian particles in arrays of closely confining microchannels permeated by a variety of attractive optical potentials and connecting two baths with equal particle concentration. We simultaneously test free diffusion in the channel, diffusion in optical traps coupled in the center of the channel, and diffusion in traps extending into the baths. We found that both classes of attractive optical potentials enhance the translocation rate through the channel with respect to free diffusion. Surprisingly, for the latter class of potentials we measure a 40-fold enhancement in the translocation rate with respect to free diffusion and find a sublinear power law dependence of the translocation rate on the average number of particles in the channel. Our results reveal the function of particle binding at the channel entrances for diffusive transport and open the way to a better understanding of membrane transport and design of synthetic membranes with enhanced diffusion rate.

  5. Channel-facilitated diffusion boosted by particle binding at the channel entrance.

    PubMed

    Pagliara, Stefano; Dettmer, Simon L; Keyser, Ulrich F

    2014-07-25

    We investigate single-file diffusion of Brownian particles in arrays of closely confining microchannels permeated by a variety of attractive optical potentials and connecting two baths with equal particle concentration. We simultaneously test free diffusion in the channel, diffusion in optical traps coupled in the center of the channel, and diffusion in traps extending into the baths. We found that both classes of attractive optical potentials enhance the translocation rate through the channel with respect to free diffusion. Surprisingly, for the latter class of potentials we measure a 40-fold enhancement in the translocation rate with respect to free diffusion and find a sublinear power law dependence of the translocation rate on the average number of particles in the channel. Our results reveal the function of particle binding at the channel entrances for diffusive transport and open the way to a better understanding of membrane transport and design of synthetic membranes with enhanced diffusion rate.

  6. Kinetics of Coloration in Photochromic Tungsten(VI) Oxide/Silicon Oxycarbide/Silica Hybrid Xerogel: Insight into Cation Self-diffusion Mechanisms.

    PubMed

    Adachi, Kenta; Tokushige, Masataka; Omata, Kaoru; Yamazaki, Suzuko; Iwadate, Yoshiaki

    2016-06-01

    Silicon oxycarbide/silica composites with well-dispersed tungsten(VI) oxide (WO3) nanoparticles were obtained as transparent hybrid xerogels via an acid-catalyzed sol-gel process (hydrolysis/condensation polymerization) of 3-(triethoxysilyl)propyl methacrylate (TESPMA) and tetraethoxysilane (TEOS). The self-diffusion mechanism of alkali-metal cations and the kinetics of the photochromic coloration process in the WO3/TESPMA/TEOS hybrid xerogel systems have been systematically investigated. Under continuous UV illumination, a gradual color change (colorless → blue) corresponding to the reduction of W(6+) into W(5+) states in WO3 nanoparticles can be confirmed from the WO3/TESPMA/TEOS hybrid xerogels containing alkali-metal sulfates, although no coloration of the hybrid xerogel without alkali-metal sulfate was observed. The coloration behavior depended exclusively on a variety of alkali-metal cations present in the hybrid xerogel system. Furthermore, a detailed analysis of the self-diffusion mechanism confirmed that the alkali-metal cations electrostatically interact with a layer of unreacted silanol groups on the TESPMA/TEOS matrix surface, and subsequently pass through the interconnected pore network of the hybrid xerogel. More interestingly, in the context of an Arrhenius analysis, we found a good coincidence between the activation energies for alkali-metal cation self-diffusion and UV-induced coloration in the WO3/TESPMA/TEOS hybrid xerogel system containing the corresponding alkali-metal sulfate. It is experimentally obvious that the photochromic properties are dominated by the diffusion process of alkali-metal cations in the WO3/TESPMA/TEOS hybrid xerogel system. Such hybrid materials with cation-controlled photochromic properties will show promising prospects in applications demanding energy-efficient "smart windows" and "smart glasses". PMID:27159661

  7. Isotopic mass-dependence of metal cation diffusion coefficients in liquid water

    SciTech Connect

    Bourg, I.C.; Richter, F.M.; Christensen, J.N.; Sposito, G.

    2009-01-11

    Isotope distributions in natural systems can be highly sensitive to the mass (m) dependence of solute diffusion coefficients (D) in liquid water. Isotope geochemistry studies routinely have assumed that this mass dependence either is negligible (as predicted by hydrodynamic theories) or follows a kinetic-theory-like inverse square root relationship (D {proportional_to} m{sup -0.5}). However, our recent experimental results and molecular dynamics (MD) simulations showed that the mass dependence of D is intermediate between hydrodynamic and kinetic theory predictions (D {proportional_to} m{sup -{beta}} with 0 {<=} {beta} < 0.2 for Li{sup +}, Cl{sup -}, Mg{sup 2+}, and the noble gases). In this paper, we present new MD simulations and experimental results for Na{sup +}, K{sup +}, Cs{sup +}, and Ca{sup 2+} that confirm the generality of the inverse power-law relation D {proportional_to} m{sup -{beta}}. Our new findings allow us to develop a general description of the influence of solute valence and radius on the mass dependence of D for monatomic solutes in liquid water. This mass dependence decreases with solute radius and with the magnitude of solute valence. Molecular-scale analysis of our MD simulation results reveals that these trends derive from the exponent {beta} being smallest for those solutes whose motions are most strongly coupled to solvent hydrodynamic modes.

  8. Machine Learning Based Dimensionality Reduction Facilitates Ligand Diffusion Paths Assessment: A Case of Cytochrome P450cam.

    PubMed

    Rydzewski, J; Nowak, W

    2016-04-12

    In this work we propose an application of a nonlinear dimensionality reduction method to represent the high-dimensional configuration space of the ligand-protein dissociation process in a manner facilitating interpretation. Rugged ligand expulsion paths are mapped into 2-dimensional space. The mapping retains the main structural changes occurring during the dissociation. The topological similarity of the reduced paths may be easily studied using the Fréchet distances, and we show that this measure facilitates machine learning classification of the diffusion pathways. Further, low-dimensional configuration space allows for identification of residues active in transport during the ligand diffusion from a protein. The utility of this approach is illustrated by examination of the configuration space of cytochrome P450cam involved in expulsing camphor by means of enhanced all-atom molecular dynamics simulations. The expulsion trajectories are sampled and constructed on-the-fly during molecular dynamics simulations using the recently developed memetic algorithms [ Rydzewski, J.; Nowak, W. J. Chem. Phys. 2015 , 143 ( 12 ), 124101 ]. We show that the memetic algorithms are effective for enforcing the ligand diffusion and cavity exploration in the P450cam-camphor complex. Furthermore, we demonstrate that machine learning techniques are helpful in inspecting ligand diffusion landscapes and provide useful tools to examine structural changes accompanying rare events. PMID:26989997

  9. Diffusion or bulk flow: how plasmodesmata facilitate pre-phloem transport of assimilates.

    PubMed

    Schulz, Alexander

    2015-01-01

    Assimilates synthesized in the mesophyll of mature leaves move along the pre-phloem transport pathway to the bundle sheath of the minor veins from which they are loaded into the phloem. The present review discusses the most probable driving force(s) for the pre-phloem pathway, diffusion down the concentration gradient or bulk flow along a pressure gradient. The driving force seems to depend on the mode of phloem loading. In a majority of plant species phloem loading is a thermodynamically active process, involving the activity of membrane transporters in the sieve-element companion cell complex. Since assimilate movement includes an apoplasmic step, this mode is called apoplasmic loading. Well established is also the polymer-trap loading mode, where the phloem-transport sugars are raffinose-family oligomers in herbaceous plants. Also this mode depends on the investment of energy, here for sugar oligomerization, and leads to a high sugar accumulation in the phloem, even though the phloem is not symplasmically isolated, but well coupled by plasmodesmata (PD). Hence the mode polymer-trap mode is also designated active symplasmic loading. For woody angiosperms and gymnosperms an alternate loading mode is currently matter of discussion, called passive symplasmic loading. Based on the limited material available, this review compares the different loading modes and suggests that diffusion is the driving force in apoplasmic loaders, while bulk flow plays an increasing role in plants having a continuous symplasmic pathway from mesophyll to sieve elements. Crucial for the driving force is the question where water enters the pre-phloem pathway. Surprisingly, the role of PD in water movement has not been addressed so far appropriately. Modeling of assimilate and water fluxes indicates that in symplasmic loaders a considerable part of water flux happens through the PD between bundle sheath and phloem. PMID:25516499

  10. Application of the diffusive gradients in thin films technique for available potassium measurement in agricultural soils: effects of competing cations on potassium uptake by the resin gel.

    PubMed

    Zhang, Yulin; Mason, Sean; McNeill, Ann; McLaughlin, Michael J

    2014-09-01

    The utilization of Amberlite (IRP-69 ion-exchange resin, 100-500 wet mesh) as the binding phase in the diffusive gradients in thin films (DGT) technique has shown potential to improve the assessment of plant-available K in soils. The binding phase has recently been optimized by using a mixed Amberlite and ferrihydrite (MAF) gel which results in linear K uptake over extended deployment periods and in solutions with higher K concentrations. As restriction of K uptake by Ca on the Amberlite based resin gel has been previously proposed, potential competing effects of Ca(2+), Mg(2+) and NH(4+) on K uptake by the MAF gel were investigated. These cations had no effect on K elution efficiency which was 85%. However, K uptake by the MAF gel was restricted in the presence of competing cations in solution. Consequently, the diffusion coefficient of K decreased in the presence of cations compared to previous studies but was stable at 1.12×10(-5)cm(2)s(-1) at 25°C regardless of cation concentrations. Uptake of K by the DGT device was affected by the presence of excessive Ca in more than 30% of twenty typical Australian agricultural soils. However, this problem could be circumvented by using a shorter deployment time than the normal 24 h. Moderate correlation of concentrations of K extracted by DGT with Colwell K (extracted by NaHCO(3), R(2)=0.69) and NH4OAc K (R(2)=0.61) indicates that DGT measures a different pool of K in soils than that measured by the standard extractants used. In addition, the MAF gel has the ability to measure Ca and Mg simultaneously. PMID:25127648

  11. Application of the diffusive gradients in thin films technique for available potassium measurement in agricultural soils: effects of competing cations on potassium uptake by the resin gel.

    PubMed

    Zhang, Yulin; Mason, Sean; McNeill, Ann; McLaughlin, Michael J

    2014-09-01

    The utilization of Amberlite (IRP-69 ion-exchange resin, 100-500 wet mesh) as the binding phase in the diffusive gradients in thin films (DGT) technique has shown potential to improve the assessment of plant-available K in soils. The binding phase has recently been optimized by using a mixed Amberlite and ferrihydrite (MAF) gel which results in linear K uptake over extended deployment periods and in solutions with higher K concentrations. As restriction of K uptake by Ca on the Amberlite based resin gel has been previously proposed, potential competing effects of Ca(2+), Mg(2+) and NH(4+) on K uptake by the MAF gel were investigated. These cations had no effect on K elution efficiency which was 85%. However, K uptake by the MAF gel was restricted in the presence of competing cations in solution. Consequently, the diffusion coefficient of K decreased in the presence of cations compared to previous studies but was stable at 1.12×10(-5)cm(2)s(-1) at 25°C regardless of cation concentrations. Uptake of K by the DGT device was affected by the presence of excessive Ca in more than 30% of twenty typical Australian agricultural soils. However, this problem could be circumvented by using a shorter deployment time than the normal 24 h. Moderate correlation of concentrations of K extracted by DGT with Colwell K (extracted by NaHCO(3), R(2)=0.69) and NH4OAc K (R(2)=0.61) indicates that DGT measures a different pool of K in soils than that measured by the standard extractants used. In addition, the MAF gel has the ability to measure Ca and Mg simultaneously.

  12. Understanding innovators' experiences of barriers and facilitators in implementation and diffusion of healthcare service innovations: a qualitative study

    PubMed Central

    2011-01-01

    Background Healthcare service innovations are considered to play a pivotal role in improving organisational efficiency and responding effectively to healthcare needs. Nevertheless, healthcare organisations encounter major difficulties in sustaining and diffusing innovations, especially those which concern the organisation and delivery of healthcare services. The purpose of the present study was to explore how healthcare innovators of process-based initiatives perceived and made sense of factors that either facilitated or obstructed the innovation implementation and diffusion. Methods A qualitative study was designed. Fifteen primary and secondary healthcare organisations in the UK, which had received health service awards for successfully generating and implementing service innovations, were studied. In-depth, semi structured interviews were conducted with the organisational representatives who conceived and led the development process. The data were recorded, transcribed and thematically analysed. Results Four main themes were identified in the analysis of the data: the role of evidence, the function of inter-organisational partnerships, the influence of human-based resources, and the impact of contextual factors. "Hard" evidence operated as a proof of effectiveness, a means of dissemination and a pre-requisite for the initiation of innovation. Inter-organisational partnerships and people-based resources, such as champions, were considered an integral part of the process of developing, establishing and diffusing the innovations. Finally, contextual influences, both intra-organisational and extra-organisational were seen as critical in either impeding or facilitating innovators' efforts. Conclusions A range of factors of different combinations and co-occurrence were pointed out by the innovators as they were reflecting on their experiences of implementing, stabilising and diffusing novel service initiatives. Even though the innovations studied were of various

  13. Cation diffusion in calcite: determining closure temperatures and the thermal history for the Allan Hills 84001 meteorite.

    PubMed

    Fisler, D K; Cygan, R T

    1998-07-01

    The presence of zoned Fe, Mg, Ca, and Mn in the carbonate phases associated with the cracks and inclusions of the Allan Hills (ALH) 84001 meteorite provides evidence for constraining the thermal history of the meteorite. Using self- and tracer-diffusion coefficients obtained from laboratory experiments on natural calcite, cooling rates are calculated for various temperatures and diffusion distances to assist in the evaluation of the compositional zoning associated with the carbonate phases in ALH 84001. The closure temperature model provides the average temperature below which compositional zoning will be preserved for a given cooling rate, that is, the temperature at which diffusion will be ineffective in homogenizing the phase. The validity of various theories for the formation of the carbonate globules may be examined, therefore, in view of the diffusion-limited kinetic constraints. Experiments using a thin film-mineral diffusion couple and ion microprobe for depth profiling analysis were performed for the temperature range of 550-800 degrees C to determine self- and tracer-diffusion coefficients for Ca and Mg and in calcite. The resulting activation energies for Ca (Ea(Ca) = 271 +/- 80 kJ/mol) and for Mg (Ea(Mg) = 284 +/- 74 kJ/mol) were used then to calculate a series of cooling rate, grain size, and closure temperature curves. The data indicate, for example, that by the diffusion of Mg in calcite, a 10 micrometers compositional zone would be completely homogenized at a temperature of 300 degrees C for cooling rates <100 K/Ma. These data provide no constraint on formation models that propose a low-temperature fluid precipitation mechanism; however, they indicate that the carbonate globules were not exposed to a high-temperature environment for long time scales following formation. PMID:11543076

  14. Cation diffusion in calcite: determining closure temperatures and the thermal history for the Allan Hills 84001 meteorite.

    PubMed

    Fisler, D K; Cygan, R T

    1998-07-01

    The presence of zoned Fe, Mg, Ca, and Mn in the carbonate phases associated with the cracks and inclusions of the Allan Hills (ALH) 84001 meteorite provides evidence for constraining the thermal history of the meteorite. Using self- and tracer-diffusion coefficients obtained from laboratory experiments on natural calcite, cooling rates are calculated for various temperatures and diffusion distances to assist in the evaluation of the compositional zoning associated with the carbonate phases in ALH 84001. The closure temperature model provides the average temperature below which compositional zoning will be preserved for a given cooling rate, that is, the temperature at which diffusion will be ineffective in homogenizing the phase. The validity of various theories for the formation of the carbonate globules may be examined, therefore, in view of the diffusion-limited kinetic constraints. Experiments using a thin film-mineral diffusion couple and ion microprobe for depth profiling analysis were performed for the temperature range of 550-800 degrees C to determine self- and tracer-diffusion coefficients for Ca and Mg and in calcite. The resulting activation energies for Ca (Ea(Ca) = 271 +/- 80 kJ/mol) and for Mg (Ea(Mg) = 284 +/- 74 kJ/mol) were used then to calculate a series of cooling rate, grain size, and closure temperature curves. The data indicate, for example, that by the diffusion of Mg in calcite, a 10 micrometers compositional zone would be completely homogenized at a temperature of 300 degrees C for cooling rates <100 K/Ma. These data provide no constraint on formation models that propose a low-temperature fluid precipitation mechanism; however, they indicate that the carbonate globules were not exposed to a high-temperature environment for long time scales following formation.

  15. Detection of diffuse glomerular lesions in rats: II. Comparison of indium-111 cationic small macromolecules with technetium-99m DTPA

    SciTech Connect

    McAfee, J.G.; Thomas, F.D.; Subramanian, G.; Schneider, R.D.; Lyons, B.; Roskopf, M.; Zapf-Longo, C.; Whaley, D.

    1986-04-01

    Dextrans with average molecular weights of 5000, 10,000, and 17,500 and inulin were rendered cationic by amination with 2-bromoethylamine hydrobromide. After limited coupling with DTPA cyclic dianhydride, they were labeled with 111In. A good correlation was found between their early renal uptake quantitated by camera-computer techniques and their renal clearance from multiple plasma samples in rats with glomerular damage induced by puromycin aminonucleoside and controls. However, there was poor correlation between the early renal uptake of these agents and the clearance of simultaneously injected (/sup 99m/Tc)DTPA. The 2-hr organ distribution and urinary excretion of these agents were compared with the corresponding values of DTPA. The differences in clearance between rats with glomerular damage and controls were greater with aminated dextran (mol wt 5000) than with DTPA, confirming previous work with infusions of nonradioactive charged dextrans and neutral inulin. The cationic dextrans appear to reflect the presence or absence of the normal anionic charge of the glomerular membrane as well as changes in filtration rate. Aminated inulin did not differentiate between controls and rats with glomerular disease any better than DTPA, probably because the number of amino groups conjugated was insufficient to produce the charge effect.

  16. Movement of Cations through Cuticles of Citrus aurantium and Acer saccharum: Diffusion Potentials in Mixed Salt Solutions.

    PubMed

    Tyree, M T; Tabor, C A; Wescott, C R

    1990-09-01

    We examined some biophysical mechanisms of ion migration across leaf cuticles enzymatically isolated from Acer saccharum L. and Citrus aurantium L. leaves. Diffusion potential measurements were used to calculate the permeabilities of Cl(-), Li(+), Na(+), and Cs(+) ions all as a ratio with respect to the permeability of K(+) in cuticles. In 2 millimolar ionic strength solutions the permeability sequence from high to low was K = Cs > Na > Li > Cl. When the outer and inner surfaces of cuticles were bathed in artificial precipitation and artificial apoplast, respectively, diffusion potentials ranging from -52 to -91 millivolts were measured (inside negative). The Goldman equation predicted that the measured potentials were enough to increase the driving force on the accumulation of heavy metals by a factor of 4 to 7. Other ions migrate with forces 3 to 10 times less than predicted by the Goldman equation for concentration differences alone. Our analysis showed that Ca(2+), and perhaps Mg(2+), might even be accumulated against concentration gradients under some circumstances. Their uptake was apparently driven by the diffusion potentials created by the outward migration of monovalent salts. We feel that future models predicting leaching of nutrients from trees during acid rain events must be modified to account for the probable influence of diffusion potentials on ion migration.

  17. Cation diffusion and hybridization effects at the Mn-GaSe(0001) reacted interface: Ab initio calculations and soft x-ray electron spectroscopy studies

    NASA Astrophysics Data System (ADS)

    Dash, S.; Joshi, N.; Drera, G.; Ghosh, P.; Magnano, E.; Bondino, F.; Galinetto, P.; Mozzati, M. C.; Salvinelli, G.; Aguekian, V.; Sangaletti, L.

    2016-03-01

    The electronic properties of the Mn:GaSe interface, produced by evaporating Mn at room temperature on a ɛ -GaSe(0001) single-crystal surface, have been studied by soft x-ray spectroscopies, and the experimental results are discussed at the light of ab initio DFT+U calculations of a model Ga1 -xMnxSe (x =0.055 ) surface alloy. Consistently with these calculations that also predict a high magnetic moment for the Mn ions (4.73 -4.83 μB), XAS measurements at the Mn L edge indicate that Mn diffuses into the lattice as a Mn2 + cation with negligible crystal-field effects. Ab initio calculations also show that the most energetically favorable lattice sites for Mn diffusion are those where Mn substitutes Ga cations in the Ga layers of the topmost Se-Ga-Ga-Se sandwich. Mn s and p states are found to strongly hybridize with Se and Ga p states, while weaker hybridization is predicted for Mn d states with Se s and p orbitals. Furthermore, unlike other Mn-doped semiconductors, there is strong interaction between the Ga -s and Mn -dz2 states. The effects of hybridization of Mn 3 d electrons with neighboring atoms are still clearly detectable from the characteristic charge-transfer satellites observed in the photoemission spectra. The Mn 3 d spectral weight in the valence band is probed by resonant photoemission spectroscopy at the Mn L edge, which also allowed an estimation of the charge transfer (Δ =2.95 eV) and Mott-Hubbard (U =6.4 eV) energies on the basis of impurity-cluster configuration-interaction model of the photoemission process. The Mott-Hubbard correlation energy U is consistent with the Ueff on-site Coulomb repulsion parameter (5.84 eV) determined for the ab initio calculations.

  18. Rapid binding of a cationic active site inhibitor to wild type and mutant mouse acetylcholinesterase: Brownian dynamics simulation including diffusion in the active site gorge.

    PubMed

    Tara, S; Elcock, A H; Kirchhoff, P D; Briggs, J M; Radic, Z; Taylor, P; McCammon, J A

    1998-12-01

    It is known that anionic surface residues play a role in the long-range electrostatic attraction between acetylcholinesterase and cationic ligands. In our current investigation, we show that anionic residues also play an important role in the behavior of the ligand within the active site gorge of acetylcholinesterase. Negatively charged residues near the gorge opening not only attract positively charged ligands from solution to the enzyme, but can also restrict the motion of the ligand once it is inside of the gorge. We use Brownian dynamics techniques to calculate the rate constant kon, for wild type and mutant acetylcholinesterase with a positively charged ligand. These calculations are performed by allowing the ligand to diffuse within the active site gorge. This is an extension of previously reported work in which a ligand was allowed to diffuse only to the enzyme surface. By setting the reaction criteria for the ligand closer to the active site, better agreement with experimental data is obtained. Although a number of residues influence the movement of the ligand within the gorge, Asp74 is shown to play a particularly important role in this function. Asp74 traps the ligand within the gorge, and in this way helps to ensure a reaction.

  19. Wetting effects versus ion pairs diffusivity: interactions of anionic surfactants with highly soluble cationic drugs and its impact on tablet dissolution.

    PubMed

    Desai, Divyakant; Wong, Benjamin; Huang, Yande; Ye, Qingmei; Guo, Hang; Huang, Ming; Timmins, Peter

    2015-07-01

    A study was conducted to develop a mechanistic understanding of dissolution of a highly soluble cationic drug, metformin hydrochloride, under the influence of anionic surfactants, sodium alkyl sulfates. The surfactants did not influence the saturated solubility of the drug, but reduced the surface tension of the dissolution media as the alkyl chain length increased. Their influence on tablet wetting based on the contact angles did not show any trend. The dissolution of 850 mg metformin hydrochloride tablets in 0.1 N HCl and pH 4.5 acetate buffer with 0.01% (w/v) sodium n-octyl sulfate (C8), sodium n-decyl sulfate (C10), or sodium n-tetradecyl sulfate (C14) was similar to the control, but was enhanced by sodium lauryl sulfate (C12). At 0.1% (w/v) concentration, the dissolution was not enhanced by C12 because the reduction in surface tension was counterbalanced by an increase in hydrophobic ion pairs that showed slower diffusivity by nuclear magnetic resonance. At 0.1% (w/v), metformin also formed an insoluble salt (1:2 molar ratios) with C10 (pH 1.2), C12, and C14 (pH 1.2 and 4.5) but not with C8. Three competing factors influenced the drug dissolution by surfactants: reduction in surface tension of the dissolution media, ion pairs with low diffusivity, and formation of an insoluble salt. PMID:26017286

  20. Huntingtin regulates Ca(2+) chemotaxis and K(+)-facilitated cAMP chemotaxis, in conjunction with the monovalent cation/H(+) exchanger Nhe1, in a model developmental system: insights into its possible role in Huntington׳s disease.

    PubMed

    Wessels, Deborah; Lusche, Daniel F; Scherer, Amanda; Kuhl, Spencer; Myre, Michael A; Soll, David R

    2014-10-01

    Huntington׳s disease is a neurodegenerative disorder, attributable to an expanded trinucleotide repeat in the coding region of the human HTT gene, which encodes the protein huntingtin. These mutations lead to huntingtin fragment inclusions in the striatum of the brain. However, the exact function of normal huntingtin and the defect causing the disease remain obscure. Because there are indications that huntingtin plays a role in Ca(2+) homeostasis, we studied the deletion mutant of the HTT ortholog in the model developmental system Dictyostelium discoideum, in which Ca(2+) plays a role in receptor-regulated behavior related to the aggregation process that leads to multicellular morphogenesis. The D. discoideum htt(-)-mutant failed to undergo both K(+)-facilitated chemotaxis in spatial gradients of the major chemoattractant cAMP, and chemotaxis up a spatial gradient of Ca(2+), but behaved normally in Ca(2+)-facilitated cAMP chemotaxis and Ca(2+)-dependent flow-directed motility. This was the same phenotypic profile of the null mutant of Nhel, a monovalent cation/H(+)exchanger. The htt(-)-mutant also failed to orient correctly during natural aggregation, as was the case for the Nhel mutant. Moreover, in a K(+)-based buffer the normal localization of actin was similarly defective in both htt(-) and nhe1(-) cells in a K(+)-based buffer, and the normal localization of Nhe1 was disrupted in the htt(-) mutant. These observations demonstrate that Htt and Nhel play roles in the same specific cation-facilitated behaviors and that Nhel localization is directly or indirectly regulated by Htt. Similar cation-dependent behaviors and a similar relationship between Htt and Nhe1 have not been reported for mammalian neurons and deserves investigation, especially as it may relate to Huntington׳s disease. PMID:25149514

  1. Huntingtin regulates Ca(2+) chemotaxis and K(+)-facilitated cAMP chemotaxis, in conjunction with the monovalent cation/H(+) exchanger Nhe1, in a model developmental system: insights into its possible role in Huntington׳s disease.

    PubMed

    Wessels, Deborah; Lusche, Daniel F; Scherer, Amanda; Kuhl, Spencer; Myre, Michael A; Soll, David R

    2014-10-01

    Huntington׳s disease is a neurodegenerative disorder, attributable to an expanded trinucleotide repeat in the coding region of the human HTT gene, which encodes the protein huntingtin. These mutations lead to huntingtin fragment inclusions in the striatum of the brain. However, the exact function of normal huntingtin and the defect causing the disease remain obscure. Because there are indications that huntingtin plays a role in Ca(2+) homeostasis, we studied the deletion mutant of the HTT ortholog in the model developmental system Dictyostelium discoideum, in which Ca(2+) plays a role in receptor-regulated behavior related to the aggregation process that leads to multicellular morphogenesis. The D. discoideum htt(-)-mutant failed to undergo both K(+)-facilitated chemotaxis in spatial gradients of the major chemoattractant cAMP, and chemotaxis up a spatial gradient of Ca(2+), but behaved normally in Ca(2+)-facilitated cAMP chemotaxis and Ca(2+)-dependent flow-directed motility. This was the same phenotypic profile of the null mutant of Nhel, a monovalent cation/H(+)exchanger. The htt(-)-mutant also failed to orient correctly during natural aggregation, as was the case for the Nhel mutant. Moreover, in a K(+)-based buffer the normal localization of actin was similarly defective in both htt(-) and nhe1(-) cells in a K(+)-based buffer, and the normal localization of Nhe1 was disrupted in the htt(-) mutant. These observations demonstrate that Htt and Nhel play roles in the same specific cation-facilitated behaviors and that Nhel localization is directly or indirectly regulated by Htt. Similar cation-dependent behaviors and a similar relationship between Htt and Nhe1 have not been reported for mammalian neurons and deserves investigation, especially as it may relate to Huntington׳s disease.

  2. 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}.

  3. A linear gradient line source facilitates the use of diffusion models with high order approximation for efficient, accurate turbid sample optical properties recovery.

    PubMed

    Lee, Ming-Wei; Hung, Cheng-Hung; Liao, Jung-Li; Cheng, Nan-Yu; Hou, Ming-Feng; Tseng, Sheng-Hao

    2014-10-01

    In this paper, we demonstrate that a scanning MEMS mirror can be employed to create a linear gradient line source that is equivalent to a planar source. This light source setup facilitates the use of diffusion models of increased orders of approximation having closed form solution, and thus enhance the efficiency and accuracy in sample optical properties recovery. In addition, compared with a regular planar light source, the linear gradient line source occupies much less source area and has an elevated measurement efficiency. We employed a δ-P1 diffusion equation with a closed form solution and carried out a phantom study to understand the performance of this new method in determining the absorption and scattering properties of turbid samples. Moreover, our Monte Carlo simulation results indicated that this geometry had probing depths comparable to those of the conventional diffuse reflectance measurement geometry with a source-detector separation of 3 mm. We expect that this new source setup would facilitate the investigating of superficial volumes of turbid samples in the wavelength regions where tissue absorption coefficients are comparable to scattering coefficients.

  4. A pH-sensitive function and phenotype: evidence that EutH facilitates diffusion of uncharged ethanolamine in Salmonella enterica.

    PubMed

    Penrod, Joseph T; Mace, Christopher C; Roth, John R

    2004-10-01

    The eutH gene is part of an operon that allows Salmonella enterica to use ethanolamine as a sole source of nitrogen, carbon, and energy. Although the sequence of EutH suggests a role in transport, eutH mutants use ethanolamine normally under standard conditions (pH 7.0). These mutants fail to use ethanolamine at a low pH. Evidence is presented that protonated ethanolamine (Eth0) does not enter cells, while uncharged ethanolamine (Eth0) diffuses freely across the membrane. The external concentration of Eth0 varies with the pH (pK=9.5). At pH 7.0, the standard ethanolamine concentration (41 mM) provides enough Eth0 for an influx rate that can support growth with or without EutH. When a lowered pH and/or ethanolamine concentration reduced the Eth0 concentration below 25 microM, EutH was needed to facilitate diffusion. EutH+ cells grew normally at Eth0 concentrations above 3 microM, close to the Km (9 microM) of the first degradative enzyme, ethanolamine ammonia lyase. It is suggested that EutH facilitates diffusion of Eth0. As predicted for a transporter, EutH contributed to the toxicity of ethanolamine seen under some conditions; furthermore, fusion of EutH to fluorescent Yfp protein provided evidence that EutH is a membrane protein.

  5. Modeling packed bed sorbent systems with the Pore Surface Diffusion Model: Evidence of facilitated surface diffusion of arsenate in nano-metal (hydr)oxide hybrid ion exchange media.

    PubMed

    Dale, Sachie; Markovski, Jasmina; Hristovski, Kiril D

    2016-09-01

    This study explores the possibility of employing the Pore Surface Diffusion Model (PSDM) to predict the arsenic breakthrough curve of a packed bed system operated under continuous flow conditions with realistic groundwater, and consequently minimize the need to conduct pilot scale tests. To provide the nano-metal (hydr)oxide hybrid ion exchange media's performance in realistic water matrices without engaging in taxing pilot scale testing, the multi-point equilibrium batch sorption tests under pseudo-equilibrium conditions were performed; arsenate breakthrough curve of short bed column (SBC) was predicted by the PSDM in the continuous flow experiments; SBC tests were conducted under the same conditions to validate the model. The overlapping Freundlich isotherms suggested that the water matrix and competing ions did not have any denoting effect on sorption capacity of the media when the matrix was changed from arsenic-only model water to real groundwater. As expected, the PSDM provided a relatively good prediction of the breakthrough profile for arsenic-only model water limited by intraparticle mass transports. In contrast, the groundwater breakthrough curve demonstrated significantly faster intraparticle mass transport suggesting to a surface diffusion process, which occurs in parallel to the pore diffusion. A simple selection of DS=1/2 DP appears to be sufficient when describing the facilitated surface diffusion of arsenate inside metal (hydr)oxide nano-enabled hybrid ion-exchange media in presence of sulfate, however, quantification of the factors determining the surface diffusion coefficient's magnitude under different treatment scenarios remained unexplored.

  6. Message spreading in networks with stickiness and persistence: Large clustering does not always facilitate large-scale diffusion

    NASA Astrophysics Data System (ADS)

    Cui, Pengbi; Tang, Ming; Wu, Zhi-Xi

    2014-09-01

    Recent empirical studies have confirmed the key roles of complex contagion mechanisms such as memory, social reinforcement, and decay effects in information diffusion and behavior spreading. Inspired by this fact, we here propose a new agent-based model to capture the whole picture of the joint action of the three mechanisms in information spreading, by quantifying the complex contagion mechanisms as stickiness and persistence, and carry out extensive simulations of the model on various networks. By numerical simulations as well as theoretical analysis, we find that the stickiness of the message determines the critical dynamics of message diffusion on tree-like networks, whereas the persistence plays a decisive role on dense regular lattices. In either network, the greater persistence can effectively make the message more invasive. Of particular interest is that our research results renew our previous knowledge that messages can spread broader in networks with large clustering, which turns out to be only true when they can inform a non-zero fraction of the population in the limit of large system size.

  7. Message spreading in networks with stickiness and persistence: Large clustering does not always facilitate large-scale diffusion

    PubMed Central

    Cui, Pengbi; Tang, Ming; Wu, Zhi-Xi

    2014-01-01

    Recent empirical studies have confirmed the key roles of complex contagion mechanisms such as memory, social reinforcement, and decay effects in information diffusion and behavior spreading. Inspired by this fact, we here propose a new agent–based model to capture the whole picture of the joint action of the three mechanisms in information spreading, by quantifying the complex contagion mechanisms as stickiness and persistence, and carry out extensive simulations of the model on various networks. By numerical simulations as well as theoretical analysis, we find that the stickiness of the message determines the critical dynamics of message diffusion on tree-like networks, whereas the persistence plays a decisive role on dense regular lattices. In either network, the greater persistence can effectively make the message more invasive. Of particular interest is that our research results renew our previous knowledge that messages can spread broader in networks with large clustering, which turns out to be only true when they can inform a non-zero fraction of the population in the limit of large system size. PMID:25200277

  8. A comparative study on the effect of Curcumin and Chlorin-p6 on the diffusion of two organic cations across a negatively charged lipid bilayer probed by second harmonic spectroscopy

    NASA Astrophysics Data System (ADS)

    Saini, R. K.; Varshney, G. K.; Dube, A.; Gupta, P. K.; Das, K.

    2014-09-01

    The influence of Curcumin and Chlorin-p6 (Cp6) on the real time diffusion kinetics of two organic cations, LDS (LDS-698) and Malachite Green (MG) across a negatively charged phospholipid bilayer is investigated by Second Harmonic (SH) spectroscopy. The diffusion time constant of LDS at neutral pH in liposomes containing either Curcumin or Cp6 is significantly reduced, the effect being more pronounced with Curcumin. At acidic pH, the quantum of reduction in the diffusion time constant of MG by both the drugs was observed to be similar. The relative changes in the average diffusion time constants of the cations with increasing drug concentration at pH 5.0 and 7.4 shows a substantial pH effect for Curcumin induced membrane permeability, while a modest pH effect was observed for Cp6 induced membrane permeability. Based on available evidence this can be attributed to the increased interaction between the drug and the polar head groups of the lipid at pH 7.4 where the drug resides closer to the lipid-water interface.

  9. Effect of cation structure on the oxygen solubility and diffusivity in a range of bis{(trifluoromethyl)sulfonyl}imide anion based ionic liquids for lithium-air battery electrolytes.

    PubMed

    Neale, Alex R; Li, Peilin; Jacquemin, Johan; Goodrich, Peter; Ball, Sarah C; Compton, Richard G; Hardacre, Christopher

    2016-04-28

    This paper reports on the solubility and diffusivity of dissolved oxygen in a series of ionic liquids (ILs) based on the bis{(trifluoromethyl)sulfonyl}imide anion with a range of related alkyl and ether functionalised cyclic alkylammonium cations. Cyclic voltammetry has been used to observe the reduction of oxygen in ILs at a microdisk electrode and chronoamperometric measurements have then been applied to simultaneously determine both the concentration and the diffusion coefficient of oxygen in different ILs. The viscosity of the ILs and the calculated molar volume and free volume are also reported. It is found that, within this class of ILs, the oxygen diffusivity generally increases with decreasing viscosity of the neat IL. An inverse relationship between oxygen solubility and IL free volume is reported for the two IL families implying that oxygen is not simply occupying the available empty space. In addition, it is reported that the introduction of an ether-group into the IL cation structure promotes the diffusivity of dissolved oxygen but reduces the solubility of the gas. PMID:27052672

  10. Reptation-induced coalescence of tunnels and cavities in Escherichia Coli XylE transporter conformers accounts for facilitated diffusion.

    PubMed

    Cunningham, Philip; Naftalin, Richard J

    2014-11-01

    Structural changes and xylose docking to eight conformers of Escherichia Coli XylE, a xylose transporter similar to mammalian passive glucose transporters GLUTs, have been examined. Xylose docks to inward and outward facing conformers at a high affinity central site (K(i) 4-20 µM), previously identified by crystallography and additionally consistently docks to lower affinity sites in the external and internal vestibules (K(i) 12-50 µM). All these sites lie within intramolecular tunnels and cavities. Several local regions in the central transmembrane zone have large positional divergences of both skeleton carbon Cα positions and side chains. One such in TM 10 is the destabilizing sequence G388-P389-V390-C391 with an average RMSD (4.5 ± 0.4 Å). Interchange between conformer poses results in coalescence of tunnels with adjacent cavities, thereby producing a transitory channel spanning the entire transporter. A fully open channel exists in one inward-facing apo-conformer, (PDB 4ja4c) as demonstrated by several different tunnel-finding algorithms. The conformer interchanges produce a gated network within a branched central channel that permits staged ligand diffusion across the transporter during the open gate periods. Simulation of this model demonstrates that small-scale conformational changes required for sequentially opening gate with frequencies in the ns-μs time domain accommodate diffusive ligand flow between adjacent sites with association-dissociation rates in the μs-ms domain without imposing delays. This current model helps to unify the apparently opposing concepts of alternate access and multisite models of ligand transport.

  11. Reptation-induced coalescence of tunnels and cavities in Escherichia Coli XylE transporter conformers accounts for facilitated diffusion.

    PubMed

    Cunningham, Philip; Naftalin, Richard J

    2014-11-01

    Structural changes and xylose docking to eight conformers of Escherichia Coli XylE, a xylose transporter similar to mammalian passive glucose transporters GLUTs, have been examined. Xylose docks to inward and outward facing conformers at a high affinity central site (K(i) 4-20 µM), previously identified by crystallography and additionally consistently docks to lower affinity sites in the external and internal vestibules (K(i) 12-50 µM). All these sites lie within intramolecular tunnels and cavities. Several local regions in the central transmembrane zone have large positional divergences of both skeleton carbon Cα positions and side chains. One such in TM 10 is the destabilizing sequence G388-P389-V390-C391 with an average RMSD (4.5 ± 0.4 Å). Interchange between conformer poses results in coalescence of tunnels with adjacent cavities, thereby producing a transitory channel spanning the entire transporter. A fully open channel exists in one inward-facing apo-conformer, (PDB 4ja4c) as demonstrated by several different tunnel-finding algorithms. The conformer interchanges produce a gated network within a branched central channel that permits staged ligand diffusion across the transporter during the open gate periods. Simulation of this model demonstrates that small-scale conformational changes required for sequentially opening gate with frequencies in the ns-μs time domain accommodate diffusive ligand flow between adjacent sites with association-dissociation rates in the μs-ms domain without imposing delays. This current model helps to unify the apparently opposing concepts of alternate access and multisite models of ligand transport. PMID:25163893

  12. Modeling packed bed sorbent systems with the Pore Surface Diffusion Model: Evidence of facilitated surface diffusion of arsenate in nano-metal (hydr)oxide hybrid ion exchange media.

    PubMed

    Dale, Sachie; Markovski, Jasmina; Hristovski, Kiril D

    2016-09-01

    This study explores the possibility of employing the Pore Surface Diffusion Model (PSDM) to predict the arsenic breakthrough curve of a packed bed system operated under continuous flow conditions with realistic groundwater, and consequently minimize the need to conduct pilot scale tests. To provide the nano-metal (hydr)oxide hybrid ion exchange media's performance in realistic water matrices without engaging in taxing pilot scale testing, the multi-point equilibrium batch sorption tests under pseudo-equilibrium conditions were performed; arsenate breakthrough curve of short bed column (SBC) was predicted by the PSDM in the continuous flow experiments; SBC tests were conducted under the same conditions to validate the model. The overlapping Freundlich isotherms suggested that the water matrix and competing ions did not have any denoting effect on sorption capacity of the media when the matrix was changed from arsenic-only model water to real groundwater. As expected, the PSDM provided a relatively good prediction of the breakthrough profile for arsenic-only model water limited by intraparticle mass transports. In contrast, the groundwater breakthrough curve demonstrated significantly faster intraparticle mass transport suggesting to a surface diffusion process, which occurs in parallel to the pore diffusion. A simple selection of DS=1/2 DP appears to be sufficient when describing the facilitated surface diffusion of arsenate inside metal (hydr)oxide nano-enabled hybrid ion-exchange media in presence of sulfate, however, quantification of the factors determining the surface diffusion coefficient's magnitude under different treatment scenarios remained unexplored. PMID:26672387

  13. Uptake of L-nicotine and of 6-hydroxy-L-nicotine by Arthrobacter nicotinovorans and by Escherichia coli is mediated by facilitated diffusion and not by passive diffusion or active transport.

    PubMed

    Ganas, Petra; Brandsch, Roderich

    2009-06-01

    The mechanism by which l-nicotine is taken up by bacteria that are able to grow on it is unknown. Nicotine degradation by Arthrobacter nicotinovorans, a Gram-positive soil bacterium, is linked to the presence of the catabolic megaplasmid pAO1. l-[(14)C]Nicotine uptake assays with A. nicotinovorans showed transport of nicotine across the cell membrane to be energy-independent and saturable with a K(m) of 6.2+/-0.1 microM and a V(max) of 0.70+/-0.08 micromol min(-1) (mg protein)(-1). This is in accord with a mechanism of facilitated diffusion, driven by the nicotine concentration gradient. Nicotine uptake was coupled to its intracellular degradation, and an A. nicotinovorans strain unable to degrade nicotine (pAO1(-)) showed no nicotine import. However, when the nicotine dehydrogenase genes were expressed in this strain, import of l-[(14)C]nicotine took place. A. nicotinovorans pAO1(-) and Escherichia coli were also unable to import 6-hydroxy-l-nicotine, but expression of the 6-hydroxy-l-nicotine oxidase gene allowed both bacteria to take up this compound. l-Nicotine uptake was inhibited by d-nicotine, 6-hydroxy-l-nicotine and 2-amino-l-nicotine, which may indicate transport of these nicotine derivatives by a common permease. Attempts to correlate nicotine uptake with pAO1 genes possessing similarity to amino acid transporters failed. In contrast to the situation at the blood-brain barrier, nicotine transport across the cell membrane by these bacteria was not by passive diffusion or active transport but by facilitated diffusion.

  14. Maize plasma membrane aquaporin ZmPIP2;5, but not ZmPIP1;2, facilitates transmembrane diffusion of hydrogen peroxide.

    PubMed

    Bienert, Gerd P; Heinen, Robert B; Berny, Marie C; Chaumont, François

    2014-01-01

    Plant aquaporins play important roles in transmembrane water transport processes, but some also facilitate the diffusion of other small uncharged solutes ranging from gases to metalloids. Recent evidence suggests that the transmembrane movement of hydrogen peroxide, an intra- and intercellular multifunctional signaling and defense compound, can be regulated by aquaporins. We addressed the question whether maize aquaporins belonging to the plasma membrane intrinsic protein (PIP) subfamily facilitate hydrogen peroxide diffusion using heterologous expression in the yeast Saccharomyces cerevisiae. We showed that ZmPIP proteins belonging to the PIP1 and PIP2 groups were significantly expressed in yeast cells only after codon optimization of their cDNA. In accordance with previous localization studies in oocytes and plants, ZmPIP1;2 was mainly retained in intracellular membranes, while ZmPIP2;5 was localized to the plasma membrane. However, upon co-expression with ZmPIP2;5, ZmPIP1;2 was re-localized to the plasma membrane. Using a non-functional plasma membrane-localized ZmPIP2;5 mutant to deliver ZmPIP1;2 to the plasma membrane, we demonstrated that, in contrast to wild type ZmPIP2;5, ZmPIP1;2 was not permeable to hydrogen peroxide. Our study further highlighted the fact that, when using the yeast system, which is widely employed to study substrates for plant aquaporins and other transporters, although positive transport assay results allow direct conclusions to be drawn regarding solute permeability, negative results require additional control experiments to show that the protein is expressed and localized correctly before concluding on the lack of transport activity.

  15. Highly precise detection, discrimination, and removal of anionic surfactants over the full pH range via cationic conjugated polymer: an efficient strategy to facilitate illicit-drug analysis.

    PubMed

    Hussain, Sameer; Malik, Akhtar H; Iyer, Parameswar K

    2015-02-11

    A water-soluble cationic conjugated polyelectrolyte (CPE), poly(1,4-bis(6-(1-methylimidazolium)-hexyloxy)-benzene bromide) (PMI) displays extraordinary stability over the full pH range of 1-14 as well as in seawater, brine, urine, and other solutions and carries out efficient detection, discrimination, and removal of moderately dissimilar anionic surfactants (viz., sodium dodecyl benzenesulfonate (SDBS) and sodium dodecyl sulfate (SDS)) at very low levels (31.7 and 17.3 parts per billion (ppb), respectively). PMI formed stable hydrogels in the presence of SDS that remained unaffected by strong acids/bases, heating, ultrasonication, or exposure to light, whereas SDBS formed precipitate with PMI as a result of its different interpolymer cofacial arrangement via Columbic attraction. The complex-forming ability of PMI with SDS and SDBS facilitated their elimination from water or drug-doped urine samples without the use of any organic solvent, chromatographic technique, or solid support. This protocol, the first of its kind for the removal of anionic surfactants at very low concentrations from any type of solution and competitive environments, demonstrates an original application using a CPE. The surfactant-free sample solutions could be precisely analyzed for the presence of illicit drugs by any standard methods. Using PMI, a newly developed CPE, a rapid and practical method for the efficient detection, discrimination, and removal of SDS and SDBS at ppb levels from water and urine, under harsh conditions, and in natural chemical environments is demonstrated.

  16. Highly precise detection, discrimination, and removal of anionic surfactants over the full pH range via cationic conjugated polymer: an efficient strategy to facilitate illicit-drug analysis.

    PubMed

    Hussain, Sameer; Malik, Akhtar H; Iyer, Parameswar K

    2015-02-11

    A water-soluble cationic conjugated polyelectrolyte (CPE), poly(1,4-bis(6-(1-methylimidazolium)-hexyloxy)-benzene bromide) (PMI) displays extraordinary stability over the full pH range of 1-14 as well as in seawater, brine, urine, and other solutions and carries out efficient detection, discrimination, and removal of moderately dissimilar anionic surfactants (viz., sodium dodecyl benzenesulfonate (SDBS) and sodium dodecyl sulfate (SDS)) at very low levels (31.7 and 17.3 parts per billion (ppb), respectively). PMI formed stable hydrogels in the presence of SDS that remained unaffected by strong acids/bases, heating, ultrasonication, or exposure to light, whereas SDBS formed precipitate with PMI as a result of its different interpolymer cofacial arrangement via Columbic attraction. The complex-forming ability of PMI with SDS and SDBS facilitated their elimination from water or drug-doped urine samples without the use of any organic solvent, chromatographic technique, or solid support. This protocol, the first of its kind for the removal of anionic surfactants at very low concentrations from any type of solution and competitive environments, demonstrates an original application using a CPE. The surfactant-free sample solutions could be precisely analyzed for the presence of illicit drugs by any standard methods. Using PMI, a newly developed CPE, a rapid and practical method for the efficient detection, discrimination, and removal of SDS and SDBS at ppb levels from water and urine, under harsh conditions, and in natural chemical environments is demonstrated. PMID:25588321

  17. 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.

  18. Electronic spectra of astrophysically interesting cations

    SciTech Connect

    Maier, John P. Rice, Corey A. Mazzotti, Fabio J. Johnson, Anatoly

    2015-01-22

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

  19. Multivalent binding and facilitated diffusion account for the formation of the Grb2-Sos1 signaling complex in a cooperative manner.

    PubMed

    McDonald, Caleb B; Balke, Jordan E; Bhat, Vikas; Mikles, David C; Deegan, Brian J; Seldeen, Kenneth L; Farooq, Amjad

    2012-03-13

    Despite its key role in driving cellular growth and proliferation through receptor tyrosine kinase (RTK) signaling, the Grb2-Sos1 macromolecular interaction remains poorly understood in mechanistic terms. Herein, using an array of biophysical methods, we provide evidence that although the Grb2 adaptor can potentially bind to all four PXψPXR motifs (designated herein S1-S4) located within the Sos1 guanine nucleotide exchange factor, the formation of the Grb2-Sos1 signaling complex occurs with a 2:1 stoichiometry. Strikingly, such bivalent binding appears to be driven by the association of the Grb2 homodimer to only two of four potential PXψPXR motifs within Sos1 at any one time. Of particular interest is the observation that of a possible six pairwise combinations in which S1-S4 motifs may act in concert for the docking of the Grb2 homodimer through bivalent binding, only S1 and S3, S1 and S4, S2 and S4, and S3 and S4 do so, while pairwise combinations of sites S1 and S2 and sites S2 and S3 appear to afford only monovalent binding. This salient observation implicates the role of local physical constraints in fine-tuning the conformational heterogeneity of the Grb2-Sos1 signaling complex. Importantly, the presence of multiple binding sites within Sos1 appears to provide a physical route for Grb2 to hop in a flip-flop manner from one site to the next through facilitated diffusion, and such rapid exchange forms the basis of positive cooperativity driving the bivalent binding of Grb2 to Sos1 with high affinity. Collectively, our study sheds new light on the assembly of a key macromolecular signaling complex central to cellular machinery in health and disease. PMID:22360309

  20. Glycerol uptake is by passive diffusion in the heart but by facilitated transport in RBCs at high glycerol levels in cold acclimated rainbow smelt (Osmerus mordax).

    PubMed

    Clow, Kathy A; Driedzic, William R

    2012-04-15

    Rainbow smelt (Osmerus mordax) is a small fish that accumulates glycerol at low winter seawater temperatures. In laboratory-held fish, glycerol concentration typically reaches 225 mM in plasma and in all cells. Glycerol uptake by the heart and red blood cells (RBCs) was assessed by tracking [(14)C(U)]glycerol into the acid-soluble pool. In fish acclimated to 9-10°C a decrease in perfusion/incubation temperature from 8 to 1°C resulted in a decrease in glycerol uptake with a Q(10) of 3.2 in heart and 2.4 in RBCs. Acclimation to ∼1.5°C did not result in an adaptive enhancement of glycerol uptake as rates were unchanged in heart and RBCs. Glycerol uptake at 1°C was by passive diffusion in heart as evidenced by a linear relationship between glycerol uptake and extracellular glycerol concentration and a lack of inhibition by phloretin. In contrast, in RBCs, glycerol uptake with respect to glycerol concentration showed two linear relationships with a transition point around 50 mM extracellular glycerol. The slope of the second phase was much steeper and eliminated with the inclusion of phloretin. In RBCs from Atlantic salmon (Salmo salar), a related species that does not accumulate glycerol, glycerol uptake showed only a single linear curve and was not inhibited by phloretin. The data imply a strong facilitated component to glycerol uptake in rainbow smelt RBCs at high glycerol concentrations. We propose this is related to cyclic changes in RBC glycerol content involving a loss of glycerol at the gill and a reaccumulation during passage through the liver. PMID:22319051

  1. Glycerol uptake is by passive diffusion in the heart but by facilitated transport in RBCs at high glycerol levels in cold acclimated rainbow smelt (Osmerus mordax).

    PubMed

    Clow, Kathy A; Driedzic, William R

    2012-04-15

    Rainbow smelt (Osmerus mordax) is a small fish that accumulates glycerol at low winter seawater temperatures. In laboratory-held fish, glycerol concentration typically reaches 225 mM in plasma and in all cells. Glycerol uptake by the heart and red blood cells (RBCs) was assessed by tracking [(14)C(U)]glycerol into the acid-soluble pool. In fish acclimated to 9-10°C a decrease in perfusion/incubation temperature from 8 to 1°C resulted in a decrease in glycerol uptake with a Q(10) of 3.2 in heart and 2.4 in RBCs. Acclimation to ∼1.5°C did not result in an adaptive enhancement of glycerol uptake as rates were unchanged in heart and RBCs. Glycerol uptake at 1°C was by passive diffusion in heart as evidenced by a linear relationship between glycerol uptake and extracellular glycerol concentration and a lack of inhibition by phloretin. In contrast, in RBCs, glycerol uptake with respect to glycerol concentration showed two linear relationships with a transition point around 50 mM extracellular glycerol. The slope of the second phase was much steeper and eliminated with the inclusion of phloretin. In RBCs from Atlantic salmon (Salmo salar), a related species that does not accumulate glycerol, glycerol uptake showed only a single linear curve and was not inhibited by phloretin. The data imply a strong facilitated component to glycerol uptake in rainbow smelt RBCs at high glycerol concentrations. We propose this is related to cyclic changes in RBC glycerol content involving a loss of glycerol at the gill and a reaccumulation during passage through the liver.

  2. Efficacy of HGF carried by ultrasound microbubble-cationic nano-liposomes complex for treating hepatic fibrosis in a bile duct ligation rat model, and its relationship with the diffusion-weighted MRI parameters.

    PubMed

    Zhang, Shou-hong; Wen, Kun-ming; Wu, Wei; Li, Wen-yan; Zhao, Jian-nong

    2013-12-01

    Hepatic fibrosis is a major consequence of liver aggression. Finding novel ways for counteracting this damaging process, and for evaluating fibrosis with a non-invasive imaging approach, represent important therapeutic and diagnostic challenges. Hepatocyte growth factor (HGF) is an anti-fibrosis cell growth factor that induces apoptosis in activated hepatic stellate cells, reduces excessive collagen deposition, and stimulates hepatocyte regeneration. Thus, using HGF in gene therapy against liver fibrosis is an attractive approach. The aims of the present study were: (i) to explore the efficacy of treating liver fibrosis using HGF expression vector carried by a novel ultrasound microbubble delivery system; (ii) to explore the diagnostic interest of diffusion-weighted MRI (DWI-MRI) in evaluating liver fibrosis. We established a rat model of hepatic fibrosis. The rats were administered HGF linked to novel ultrasound micro-bubbles. Progression of hepatic fibrosis was evaluated by histopathology, hydroxyproline content, and DWI-MRI to determine the apparent diffusion coefficient (ADC). Our targeted gene therapy produced a significant anti-fibrosis effect, as shown by liver histology and significant reduction of hydroxyproline content. Moreover, using DWI-MRI, the b value (diffusion gradient factor) was equal to 300s/mm(2), and the ADC values significantly decreased as the severity of hepatic fibrosis increased. Using this methodology, F0-F2 could be distinguished from F3 and F4 (P<0.01). This is the first in vivo report of using an ultrasound microbubble-cationic nano-liposome complex for gene delivery. The data indicate that, this approach is efficient to counteract the fibrosis process. DWI-MRI appears a promising imaging technique for evaluating liver fibrosis.

  3. 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

  4. Electrochemically influenced cation inter-diffusion and Co3O4 formation on La0.6Sr0.4CoO3 infiltrated into SOFC cathodes

    DOE PAGES

    Song, Xueyan; Lee, Shiwoo; Chen, Yun; Gerdes, Kirk

    2015-06-18

    Nanosized LSC electrocatalyst was infiltrated into a porous scaffold cathode composed of Sm2O3-doped CeO2 (SDC) and La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) in a commercial button solid oxide fuel cell (SOFC). To understand the stability of cathodes infiltrated with LSC, the infiltrated composite cells were subjected to both electrochemical operating and thermal aging states at 750 °C for 1500 h. Nanostructure and local chemistry evolution of La0.6Sr0.4CoO3 (LSC) infiltrated cathodes upon operation and aging were investigated by transmission electron microscopy. After operation, the LSC remained a cubic perovskite, and the crystal grains exhibit comparable size to as-infiltrated LSC grains. Inter-diffusion of Fe from themore » LSCF to a Fe-incorporated LSC layer developed on the LSCF backbone. However, only sharp interfaces were observed between LSC and SDC backbone in the as-infiltrated cathode and such interfaces remain after operation. The infiltrated LSC on the SDC backbone also retains granular particle morphology. Furthermore, newly grown Co3O4 nanocrystals were found in the operated cathode. After thermal aging, on the other hand, cation inter-diffusion across the interfaces of the infiltrate particles and the cathode backbones is less than that from the operated cells. Lastly, the following hypothesis is proposed: Co3O4 forms on LSC arising from local charge balancing between cobalt and oxygen vacancies.« less

  5. Selective cation exchange in the core region of Cu2-xSe/Cu2-xS core/shell nanocrystals.

    PubMed

    Miszta, Karol; Gariano, Graziella; Brescia, Rosaria; Marras, Sergio; De Donato, Francesco; Ghosh, Sandeep; De Trizio, Luca; Manna, Liberato

    2015-09-30

    We studied cation exchange (CE) in core/shell Cu2-xSe/Cu2-xS nanorods with two cations, Ag(+) and Hg(2+), which are known to induce rapid exchange within metal chalcogenide nanocrystals (NCs) at room temperature. At the initial stage of the reaction, the guest ions diffused through the Cu2-xS shell and reached the Cu2-xSe core, replacing first Cu(+) ions within the latter region. These experiments prove that CE in copper chalcogenide NCs is facilitated by the high diffusivity of guest cations in the lattice, such that they can probe the whole host structure and identify the preferred regions where to initiate the exchange. For both guest ions, CE is thermodynamically driven as it aims for the formation of the chalcogen phase characterized by the lower solubility under the specific reaction conditions. PMID:26360611

  6. Selective Cation Exchange in the Core Region of Cu2–xSe/Cu2–xS Core/Shell Nanocrystals

    PubMed Central

    2015-01-01

    We studied cation exchange (CE) in core/shell Cu2–xSe/Cu2–xS nanorods with two cations, Ag+ and Hg2+, which are known to induce rapid exchange within metal chalcogenide nanocrystals (NCs) at room temperature. At the initial stage of the reaction, the guest ions diffused through the Cu2–xS shell and reached the Cu2–xSe core, replacing first Cu+ ions within the latter region. These experiments prove that CE in copper chalcogenide NCs is facilitated by the high diffusivity of guest cations in the lattice, such that they can probe the whole host structure and identify the preferred regions where to initiate the exchange. For both guest ions, CE is thermodynamically driven as it aims for the formation of the chalcogen phase characterized by the lower solubility under the specific reaction conditions. PMID:26360611

  7. Selective cation exchange in the core region of Cu2-xSe/Cu2-xS core/shell nanocrystals.

    PubMed

    Miszta, Karol; Gariano, Graziella; Brescia, Rosaria; Marras, Sergio; De Donato, Francesco; Ghosh, Sandeep; De Trizio, Luca; Manna, Liberato

    2015-09-30

    We studied cation exchange (CE) in core/shell Cu2-xSe/Cu2-xS nanorods with two cations, Ag(+) and Hg(2+), which are known to induce rapid exchange within metal chalcogenide nanocrystals (NCs) at room temperature. At the initial stage of the reaction, the guest ions diffused through the Cu2-xS shell and reached the Cu2-xSe core, replacing first Cu(+) ions within the latter region. These experiments prove that CE in copper chalcogenide NCs is facilitated by the high diffusivity of guest cations in the lattice, such that they can probe the whole host structure and identify the preferred regions where to initiate the exchange. For both guest ions, CE is thermodynamically driven as it aims for the formation of the chalcogen phase characterized by the lower solubility under the specific reaction conditions.

  8. Method for the analysis of contribution of sliding and hopping to a facilitated diffusion of DNA-binding protein: Application to in vivo data

    NASA Astrophysics Data System (ADS)

    Tabaka, Marcin; Burdzy, Krzysztof; Hołyst, Robert

    2015-08-01

    DNA-binding protein searches for its target, a specific site on DNA, by means of diffusion. The search process consists of many recurrent steps of one-dimensional diffusion (sliding) along the DNA chain and three-dimensional diffusion (hopping) after dissociation of a protein from the DNA chain. Here we propose a computational method that allows extracting the contribution of sliding and hopping to the search process in vivo from the measurements of the kinetics of the target search by the lac repressor in Escherichia coli [P. Hammar et al., Science 336, 1595 (2012), 10.1126/science.1221648]. The method combines lattice Monte Carlo simulations with the Brownian excursion theory and includes explicitly steric constraints for hopping due to the helical structure of DNA. The simulation results including all experimental data reveal that the in vivo target search is dominated by sliding. The short-range hopping to the same base pair interrupts one-dimensional sliding while long-range hopping does not contribute significantly to the kinetics of the search of the target in vivo.

  9. Tobacco mosaic virus (TMV) replicase and movement protein function synergistically in facilitating TMV spread by lateral diffusion in the plasmodesmal desmotubule of Nicotiana benthamiana.

    PubMed

    Guenoune-Gelbart, Dana; Elbaum, Michael; Sagi, Guy; Levy, Amit; Epel, Bernard L

    2008-03-01

    Virus spread through plasmodesmata (Pd) is mediated by virus-encoded movement proteins (MPs) that modify Pd structure and function. The MP of Tobacco mosaic virus ((TMV)MP) is an endoplasmic reticulum (ER) integral membrane protein that binds viral RNA (vRNA), forming a vRNA:MP:ER complex. It has been hypothesized that (TMV)MP causes Pd to dilate, thus potentiating a cytoskeletal mediated sliding of the vRNA:MP:ER complex through Pd; in the absence of MP, by contrast, the ER cannot move through Pd. An alternate model proposes that cell-to-cell spread takes place by diffusion of the MP:vRNA complex in the ER membranes which traverse Pd. To test these models, we measured the effect of (TMV)MP and replicase expression on cell-to-cell spread of several green fluorescent protein-fused probes: a soluble cytoplasmic protein, two ER lumen proteins, and two ER membrane-bound proteins. Our data support the diffusion model in which a complex that includes ER-embedded MP, vRNA, and other components diffuses in the ER membrane within the Pd driven by the concentration gradient between an infected cell and adjacent noninfected cells. The data also suggest that the virus replicase and MP function together in altering Pd conductivity.

  10. Computer simulation of displacement cation exchange chromatography: separation of trivalent actinides and lanthanides

    SciTech Connect

    Forsberg, C.W.

    1980-05-01

    A first-generation mathematical model of displacement cation exchange chromatography (CES) was constructed. The model incorporated the following phenomena: diffusion of cations up and down the column, diffusion of cations from the bulk liquid to the resin surface, and equilibrium of cations between liquid and solid resin beads. A limited number of experiments with rare earths using DTPA as the separation agent were undertaken to increase the current understanding of the processes involved in cation exchange chromatography. The numerical computer program based on the mathematical model was written in FORTRAN IV for use on the IBM 360 series of computers.

  11. 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

  12. Diffusion of Ca and Mg in Calcite

    SciTech Connect

    Cygan, R.T.; Fisler, D.K.

    1999-02-10

    The self-diffusion of Ca and the tracer diffusion of Mg in calcite have been experimentally measured using isotopic tracers of {sup 25}Mg and {sup 44}Ca. Natural single crystals of calcite were coated with a thermally-sputtered oxide thin film and then annealed in a CO{sub 2} gas at one atmosphere total pressure and temperatures from 550 to 800 C. Diffusion coefficient values were derived from the depth profiles obtained by ion microprobe analysis. The resultant activation energies for Mg tracer diffusion and Ca self-diffusion are respectively: E{sub a}(Mg) = 284 {+-} 74 kJ/mol and E{sub a}(Ca) = 271 {+-} 80 kJ/mol. For the temperature ranges in these experiments, the diffusion of Mg is faster than Ca. The results are generally consistent in magnitude with divalent cation diffusion rates obtained in previous studies and provide a means of interpreting the thermal histories of carbonate minerals, the mechanism of dolomitization, and other diffusion-controlled processes. The results indicate that cation diffusion in calcite is relatively slow and cations are the rate-limiting diffusing species for the deformation of calcite and carbonate rocks. Application of the calcite-dolomite geothermometer to metamorphic assemblages will be constrained by cation diffusion and cooling rates. The direct measurement of Mg tracer diffusion in calcite indicates that dolomitization is unlikely to be accomplished by Mg diffusion in the solid state but by a recrystallization process.

  13. 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.

  14. Li diffusion in zircon

    NASA Astrophysics Data System (ADS)

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

    2010-09-01

    Diffusion of Li under anhydrous conditions at 1 atm and under fluid-present elevated pressure (1.0-1.2 GPa) conditions has been measured in natural zircon. The source of diffusant for 1-atm experiments was ground natural spodumene, which was sealed under vacuum in silica glass capsules with polished slabs of zircon. An experiment using a Dy-bearing source was also conducted to evaluate possible rate-limiting effects on Li diffusion of slow-diffusing REE+3 that might provide charge balance. Diffusion experiments performed in the presence of H2O-CO2 fluid were run in a piston-cylinder apparatus, using a source consisting of a powdered mixture of spodumene, quartz and zircon with oxalic acid added to produce H2O-CO2 fluid. Nuclear reaction analysis (NRA) with the resonant nuclear reaction 7Li(p,γ)8Be was used to measure diffusion profiles for the experiments. The following Arrhenius parameters were obtained for Li diffusion normal to the c-axis over the temperature range 703-1.151°C at 1 atm for experiments run with the spodumene source: D_{text{Li}} = 7.17 × 10^{ - 7} { exp }( - 275 ± 11 {text{kJmol}}^{ - 1} /{text{RT}}){text{m}}2 {text{s}}^{ - 1}. Diffusivities are similar for transport parallel to the c-axis, indicating little anisotropy for Li diffusion in zircon. Similar Li diffusivities were also found for experiments run under fluid-present conditions and for the experiment run with the Dy-bearing source. Li diffusion is considerably faster than diffusion of other cations in zircon, with a smaller activation energy for diffusion. Although Li diffusion in zircon is comparatively rapid, zircons will be moderately retentive of Li signatures at mid-crustal metamorphic temperatures, but they are unlikely to retain this information for geologically significant times under high-grade metamorphism.

  15. Hybrid Diffusion Imaging

    PubMed Central

    Wu, Yu-Chien; Alexander, Andrew L.

    2007-01-01

    Diffusion measurements in the human central nervous system are complex to characterize and a broad spectrum of methods have been proposed. In this study, a comprehensive diffusion encoding and analysis approach, Hybrid Diffusion Imaging (HYDI), is described. The HYDI encoding scheme is composed of multiple concentric “shells” of constant diffusion-weighting, which may be used to characterize the signal behavior with low, moderate and high diffusion-weighting. HYDI facilitates the application of multiple data-analyses strategies including diffusion tensor imaging (DTI), multi-exponential diffusion measurements, diffusion spectrum imaging (DSI) and q-ball imaging (QBI). These different analysis strategies may provide complementary information. DTI measures (mean diffusivity and fractional anisotropy) may be estimated from either data in the inner shells or the entire HYDI data. Fast and slow diffusivities were estimated using a nonlinear least-squares bi-exponential fit on geometric means of the HYDI shells. DSI measurements from the entire HYDI data yield empirical model-independent diffusion information and are well-suited for characterizing tissue regions with complex diffusion behavior. DSI measurements were characterized using the zero displacement probability and the mean squared displacement. The outermost HYDI shell was analyzed using QBI analysis to estimate the orientation distribution function (ODF), which is useful for characterizing the directions of multiple fiber groups within a voxel. In this study, a HYDI encoding scheme with 102 diffusion-weighted measurements was obtained over most of the human cerebrum in under 30 minutes. PMID:17481920

  16. Role of organic cation transporters (OCTs) in the brain.

    PubMed

    Couroussé, Thomas; Gautron, Sophie

    2015-02-01

    Organic cation transporters (OCTs) are polyspecific facilitated diffusion transporters that contribute to the absorption and clearance of various physiological compounds and xenobiotics in mammals, by mediating their vectorial transport in kidney, liver or placenta cells. Unexpectedly, a corpus of studies within the last decade has revealed that these transporters also fulfill important functions within the brain. The high-affinity monoamine reuptake transporters (SERT, NET and DAT) exert a crucial role in the control of aminergic transmission by ensuring the rapid clearance of the released transmitters from the synaptic cleft and their recycling into the nerve endings. Substantiated evidence indicate that OCTs may serve in the brain as a compensatory clearance system in case of monoamine spillover after high-affinity transporter blockade by antidepressants or psychostimulants, and in areas of lower high-affinity transporter density at distance from the aminergic varicosities. In spite of similar anatomical profiles, the two brain OCTs, OCT2 and OCT3, show subtle differences in their distribution in the brain and their functional properties. These transporters contribute to shape a variety of central functions related to mood such as anxiety, response to stress and antidepressant efficacy, but are also implicated in other processes like osmoregulation and neurotoxicity. In this review, we discuss the recent knowledge and emerging concepts on the role of OCTs in the uptake of aminergic neurotransmitters in the brain and in these various physiological functions, focusing on the implications for mental health. PMID:25251364

  17. [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.

  18. 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.

  19. Cesium cation affinities and basicities

    NASA Astrophysics Data System (ADS)

    Gal, Jean-François; Maria, Pierre-Charles; Massi, Lionel; Mayeux, Charly; Burk, Peeter; Tammiku-Taul, Jaana

    2007-11-01

    This review focuses on the quantitative data related to cesium cation interaction with neutral or negatively charged ligands. The techniques used for measuring the cesium cation affinity (enthalpies, CCA), and cesium cation basicities (Gibbs free energies, CCB) are briefly described. The quantum chemical calculations methods that were specifically designed for the determination of cesium cation adduct structures and the energetic aspects of the interaction are discussed. The experimental results, obtained essentially from mass spectrometry techniques, and complemented by thermochemical data, are tabulated and commented. In particular, the correlations between cesium cation affinities and lithium cation affinities for the various kinds of ligands (rare gases, polyatomic neutral molecules, among them aromatic compounds and negative ions) serve as a basis for the interpretation of the diverse electrostatic modes of interaction. A brief account of some recent analytical applications of ion/molecule reactions with Cs+, as well as other cationization approaches by Cs+, is given.

  20. Facilitating Facilitators: Enhancing PBL through a Structured Facilitator Development Program

    ERIC Educational Resources Information Center

    Salinitri, Francine D.; Wilhelm, Sheila M.; Crabtree, Brian L.

    2015-01-01

    With increasing adoption of the problem-based learning (PBL) model, creative approaches to enhancing facilitator training and optimizing resources to maintain effective learning in small groups is essential. We describe a theoretical framework for the development of a PBL facilitator training program that uses the constructivist approach as the…

  1. Computation Of Facilitated Transport of O2 In Hemoglobin

    NASA Technical Reports Server (NTRS)

    Davis, Sanford

    1991-01-01

    Report describes computations of unsteady facilitated transport of oxygen through liquid membrane of hemoglobin. Used here, "facilitated transport" means diffusion of permeant through membrane in which that diffusion enhanced by reversible chemical reaction between permeant and membrane. In this case, reversible reactions between hemoglobin and oxygen.

  2. Radiation stability of cations in ionic liquids. 4. Task-specific antioxidant cations for nuclear separations and photolithography.

    PubMed

    Shkrob, Ilya A; Marin, Timothy W

    2013-11-27

    Three families of "task-specific" antioxidant organic cations that include designated sites to facilitate deprotonation following electronic excitation and ionization have been introduced. The deprotonation from the excited state is reversible, leading to minimal damage of the cation, whereas the deprotonation from the oxidized cation yields persistent aroxyl and trityl radicals. This protection improves radiation stability of ionic compounds in 2.5 MeV electron beam radiolysis. Apart from the use of such cations as structural components of room temperature ionic liquid (IL) diluents for nuclear separations, their ionic compounds involving bases of superacids are well suited for use as chemically amplified acid generator resists in electron beam lithography and extreme ultraviolet photolithography.

  3. Electrochemically influenced cation inter-diffusion and Co3O4 formation on La0.6Sr0.4CoO3 infiltrated into SOFC cathodes

    SciTech Connect

    Song, Xueyan; Lee, Shiwoo; Chen, Yun; Gerdes, Kirk

    2015-06-18

    Nanosized LSC electrocatalyst was infiltrated into a porous scaffold cathode composed of Sm2O3-doped CeO2 (SDC) and La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) in a commercial button solid oxide fuel cell (SOFC). To understand the stability of cathodes infiltrated with LSC, the infiltrated composite cells were subjected to both electrochemical operating and thermal aging states at 750 °C for 1500 h. Nanostructure and local chemistry evolution of La0.6Sr0.4CoO3 (LSC) infiltrated cathodes upon operation and aging were investigated by transmission electron microscopy. After operation, the LSC remained a cubic perovskite, and the crystal grains exhibit comparable size to as-infiltrated LSC grains. Inter-diffusion of Fe from the LSCF to a Fe-incorporated LSC layer developed on the LSCF backbone. However, only sharp interfaces were observed between LSC and SDC backbone in the as-infiltrated cathode and such interfaces remain after operation. The infiltrated LSC on the SDC backbone also retains granular particle morphology. Furthermore, newly grown Co3O4 nanocrystals were found in the operated cathode. After thermal aging, on the other hand, cation inter-diffusion across the interfaces of the infiltrate particles and the cathode backbones is less than that from the operated cells. Lastly, the following hypothesis is proposed: Co3O4 forms on LSC arising from local charge balancing between cobalt and oxygen vacancies.

  4. 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

  5. Toxicity of cationic lipids and cationic polymers in gene delivery.

    PubMed

    Lv, Hongtao; Zhang, Shubiao; Wang, Bing; Cui, Shaohui; Yan, Jie

    2006-08-10

    Gene therapy, as a promising therapeutics to treat genetic or acquired diseases, has achieved exciting development in the past two decades. Appropriate gene vectors can be crucial for gene transfer. Cationic lipids and polymers, the most important non-viral vectors, have many advantages over viral ones as non-immunogenic, easy to produce and not oncogenic. They hold the promise to replace viral vectors to be used in clinic. However, the toxicity is still an obstacle to the application of non-viral vectors to gene therapy. For overcoming the problem, many new cationic compounds have been developed. This article provides a review with respect to toxicity of cationic lipids and polymers in gene delivery. We evaluate the structural features of cationic compounds and summarize the relationship of toxicity and structure and hope to provide available suggestions on the development of these cationic compounds.

  6. Insights into dynamic processes of cations in pyrochlores and other complex oxides

    SciTech Connect

    Uberuaga, Blas Pedro; Perriot, Romain

    2015-08-26

    Complex oxides are critical components of many key technologies, from solid oxide fuel cells and superionics to inert matrix fuels and nuclear waste forms. In many cases, understanding mass transport is important for predicting performance and, thus, extensive effort has been devoted to understanding mass transport in these materials. However, most work has focused on the behavior of oxygen while cation transport has received relatively little attention, even though cation diffusion is responsible for many phenomena, including sintering, radiation damage evolution, and deformation processes. Here, we use accelerated molecular dynamics simulations to examine the kinetics of cation defects in one class of complex oxides, A₂B₂O₇ pyrochlore. In some pyrochlore chemistries, B cation defects are kinetically unstable, transforming to A cation defects and antisites at rates faster than they can diffuse. When this occurs, transport of B cations occurs through defect processes on the A sublattice. Further, these A cation defects, either interstitials or vacancies, can interact with antisite disorder, reordering the material locally, though this process is much more efficient for interstitials than vacancies. Whether this behavior occurs in a given pyrochlore depends on the A and B chemistry. Pyrochlores with a smaller ratio of cation radii exhibit this complex behavior, while those with larger ratios exhibit direct migration of B interstitials. Similar behavior has been reported in other complex oxides such as spinels and perovskites, suggesting that this coupling of transport between the A and B cation sublattices, while not universal, occurs in many complex oxide.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  8. 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

  9. 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.

  10. Golgi Localized Barley MTP8 Proteins Facilitate Mn Transport

    PubMed Central

    Pedas, Pai; Schiller Stokholm, Michaela; Hegelund, Josefine Nymark; Ladegård, Anne Hald; Schjoerring, Jan Kofod; Husted, Søren

    2014-01-01

    Many metabolic processes in plants are regulated by manganese (Mn) but limited information is available on the molecular mechanisms controlling cellular Mn homeostasis. In this study, a yeast assay was used to isolate and characterize two genes, MTP8.1 and MTP8.2, which encode membrane-bound proteins belonging to the cation diffusion facilitator (CDF) family in the cereal species barley (Hordeum vulgare). Transient expression in onion epidermal cells showed that MTP8.1 and MTP8.2 proteins fused to the green fluorescent protein (GFP) are localized to Golgi. When heterologously expressed in yeast, MTP8.1 and MTP8.2 were found to be Mn transporters catalysing Mn efflux in a similar manner as the Golgi localized endogenous yeast protein Pmr1p. The level of MTP8.1 transcripts in barley roots increased with external Mn supply ranging from deficiency to toxicity, while MTP8.2 transcripts decreased under the same conditions, indicating non-overlapping functions for the two genes. In barley leaves, the expression of both MTP8 genes declined in response to toxic Mn additions to the roots suggesting a role in ensuring proper delivery of Mn to Golgi. Based on the above we suggest that barley MTP8 proteins are involved in Mn loading to the Golgi apparatus and play a role in Mn homeostasis by delivering Mn to Mn-dependent enzymes and/or by facilitating Mn efflux via secretory vesicles. This study highlights the importance of MTP transporters in Mn homeostasis and is the first report of Golgi localized Mn2+ transport proteins in a monocot plant species. PMID:25486417

  11. 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

  12. Diarylferrocene tweezers for cation binding.

    PubMed

    Lima, Carlos F R A C; Fernandes, Ana M; Melo, André; Gonçalves, Luís M; Silva, Artur M S; Santos, Luís M N B F

    2015-10-01

    The host-guest chemistry of ferrocene derivatives was explored by a combined experimental and theoretical study. Several 1-arylferrocenes and 1,1'-diarylferrocenes were synthesized by the Suzuki-Miyaura cross-coupling reaction. The ability of these compounds to bind small cations in the gas phase was investigated experimentally by electrospray ionization mass spectrometry (ESI-MS). The results evidenced a noticeable ability of all 1,1'-diarylferrocenes studied to bind cations, while the same was not observed for the corresponding 1-arylferrocenes nor ferrocene. The 1,1'-diarylferrocenecation relative interaction energies were evaluated by ESI-MS and quantum chemical calculations and showed that cation binding in these systems follows electrostatic trends. It was found that, due to their unique molecular shape and smooth torsional potentials, 1,1'-diarylferrocenes can act as molecular tweezers of small-sized cations in the gas phase. PMID:26309143

  13. Electronic absorption spectrum of triacetylene cation for astronomical considerations.

    PubMed

    Chakrabarty, S; Rice, C A; Mazzotti, F J; Dietsche, R; Maier, J P

    2013-10-01

    The A(2)Πg ← X(2)Πu electronic transition (4800-6000 Å) of triacetylene cation was measured in an ion trap, where the vibrational and rotational degrees of freedom were equilibrated to 25 K. The rotational profile of the origin band is predicted by a collisional-radiative rate model under conditions expected in diffuse interstellar clouds. Variation in the density of the surrounding gas, rotational temperature, and velocity dispersion are taken into account.

  14. Selective separation of sodium ions from a mixture with phenylalanine by Donnan dialysis with a profiled sulfogroup cation exchange membrane

    NASA Astrophysics Data System (ADS)

    Vasil'eva, V. I.; Goleva, E. A.

    2013-11-01

    The possibility of separating ions of metal from a mixture with ampholyte (an amino acid) by Donnan dialysis with an MK-40 sulfogroup cation exchange membrane is demonstrated. Conditions ensuring the selectivity and intensity of the mass transfer of sodium ions from a mixture with bipolar phenylalanine ions into a diffusate containing hydrochloric acid through a cation exchange membrane are found.

  15. 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.

  16. 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.

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

    PubMed

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

    2014-07-01

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

  18. Mechanisms of impurity diffusion in rutile

    SciTech Connect

    Peterson, N.L.; Sasaki, J.

    1984-01-01

    Tracer diffusion of /sup 46/Sc, /sup 51/Cr, /sup 54/Mn, /sup 59/Fe, /sup 60/Co, /sup 63/Ni, and /sup 95/Zr, was measured as functions of crystal orientation, temperature, and oxygen partial pressure in rutile single crystals using the radioactive tracer sectioning technique. Compared to cation self-diffusion, divalent impurities (e.g., Co and Ni) diffuse extremely rapidly in TiO/sub 2/ and exhibit a large anisotropy in the diffusion behavior; divalent-impurity diffusion parallel to the c-axis is much larger than it is perpendicular to the c-axis. The diffusion of trivalent impurity ions (Sc and Cr) and tetravalent impurity ions (Zr) is similar to cation self-diffusion, as a function of temperature and of oxygen partial pressure. The divalent impurity ions Co and Ni apparently diffuse as interstitial ions along open channels parallel to the c-axis. The results suggest that Sc, Cr, and Zr ions diffuse by an interstitialcy mechanism involving the simultaneous and cooperative migration of tetravalent interstitial titanium ions and the tracer-impurity ions. Iron ions diffused both as divalent and as trivalent ions. 8 figures.

  19. Diffusion MRI

    NASA Astrophysics Data System (ADS)

    Fukuyama, Hidenao

    Recent advances of magnetic resonance imaging have been described, especially stressed on the diffusion sequences. We have recently applied the diffusion sequence to functional brain imaging, and found the appropriate results. In addition to the neurosciences fields, diffusion weighted images have improved the accuracies of clinical diagnosis depending upon magnetic resonance images in stroke as well as inflammations.

  20. Facilitating Organizational Change.

    ERIC Educational Resources Information Center

    1999

    The first of the three papers in this symposium, "Conflicts that Arise in Small Group Facilitation: A Descriptive Study of Accounts, Actions, Outcomes, and Assessments" (Judith A. Kolb, William J. Rothwell), contains self-report verbatim accounts contributed by facilitators and the results of a literature review on small group conflict. "A Test of…

  1. A Facilitation Performance Aid.

    ERIC Educational Resources Information Center

    Chevalier, Roger

    1997-01-01

    Presents a guide, derived from the Situational Leadership model, which describes the process that should be used in facilitating a group discussion. The process includes preparation, assessment, diagnosis, prescription, development, reinforcement, and follow-up. Three figures depict the Situational Leadership model, the facilitation process, and…

  2. Optimal Network Modularity for Information Diffusion

    NASA Astrophysics Data System (ADS)

    Nematzadeh, Azadeh; Ferrara, Emilio; Flammini, Alessandro; Ahn, Yong-Yeol

    2014-08-01

    We investigate the impact of community structure on information diffusion with the linear threshold model. Our results demonstrate that modular structure may have counterintuitive effects on information diffusion when social reinforcement is present. We show that strong communities can facilitate global diffusion by enhancing local, intracommunity spreading. Using both analytic approaches and numerical simulations, we demonstrate the existence of an optimal network modularity, where global diffusion requires the minimal number of early adopters.

  3. Cu3-xP Nanocrystals as a Material Platform for Near-Infrared Plasmonics and Cation Exchange Reactions

    PubMed Central

    2015-01-01

    Synthesis approaches to colloidal Cu3P nanocrystals (NCs) have been recently developed, and their optical absorption features in the near-infrared (NIR) have been interpreted as arising from a localized surface plasmon resonance (LSPR). Our pump–probe measurements on platelet-shaped Cu3-xP NCs corroborate the plasmonic character of this absorption. In accordance with studies on crystal structure analysis of Cu3P dating back to the 1970s, our density functional calculations indicate that this material is substoichiometric in copper, since the energy of formation of Cu vacancies in certain crystallographic sites is negative, that is, they are thermodynamically favored. Also, thermoelectric measurements point to a p-type behavior of the majority carriers from films of Cu3-xP NCs. It is likely that both the LSPR and the p-type character of our Cu3-xP NCs arise from the presence of a large number of Cu vacancies in such NCs. Motivated by the presence of Cu vacancies that facilitate the ion diffusion, we have additionally exploited Cu3-xP NCs as a starting material on which to probe cation exchange reactions. We demonstrate here that Cu3-xP NCs can be easily cation-exchanged to hexagonal wurtzite InP NCs, with preservation of the anion framework (the anion framework in Cu3-xP is very close to that of wurtzite InP). Intermediate steps in this reaction are represented by Cu3-xP/InP heterostructures, as a consequence of the fact that the exchange between Cu+ and In3+ ions starts from the peripheral corners of each NC and gradually evolves toward the center. The feasibility of this transformation makes Cu3-xP NCs an interesting material platform from which to access other metal phosphides by cation exchange. PMID:25960605

  4. Cationic surfactants based on ferrocene

    SciTech Connect

    Pankratov, V.A.; Kucherova, N.L.; Abramzon, A.A.

    1988-07-20

    Quaternary ammonium salts based on ferrocene were synthesized and their surface active properties were studied as potential cationic surfactants and for uses including antiknock compounds. The salts were halide and nitrate derivatives of dimethylferrocenylmethylammonium and were prepared by aminomethylation of ferrocene. Chemical reaction yields, melting points, surface tension isotherms, and other characteristics were assessed.

  5. Assessment of cation trapping by cellular acidic compartments.

    PubMed

    Marceau, François; Roy, Caroline; Bouthillier, Johanne

    2014-01-01

    All nucleated cells, from yeast to animal cells, concentrate cationic chemicals (weak bases with a pKa~8-10) into acidic cell compartments (low retro-diffusion under a protonated form at low pH=ion trapping). The proton pump vacuolar (V)-ATPase is the driving force of this pseudotransport that concerns acidic organelles (mainly late endosomes and lysosomes). The latter rapidly become swollen (osmotic vacuolization) and macroautophagic. Cation concentration in cells is not proved to involve membrane transporters, but is prevented or reversed by inhibitors of V-ATPase, such as bafilomycin A1. Lipophilicity is a major determinant of the apparent affinity of this pseudotransport because simple diffusion of the uncharged form supports it. Quinacrine is a formerly used antiparasitic drug that is intensely fluorescent, lipophilic, and a tertiary amine. The drug, at micromolar concentrations, is proposed as a superior probe for assessing cation trapping by cellular acidic compartments, being readily quantified using fluorometry in cell extracts and analyzed using microscopy and cytofluorometry (fluorescence settings for fluorescein being applicable). Further, cells respond to micromolar levels of quinacrine by autophagic accumulation (e.g., accumulation of the activated macroautophagic effector LC3 II, immunoblots), an objective and universal response to sequestered amines.

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

    PubMed

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

    2012-08-15

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

  7. Non-diffusing radiochromic micelle gel

    NASA Astrophysics Data System (ADS)

    Jordan, Kevin; Sekimoto, Masaya

    2010-11-01

    The addition of Laponite, a synthetic clay nanoparticle material to radiochromic leuco Malachite Green micelle hydrogel eliminates diffusion of the cationic dye by electrostatic binding. The clay nanoparticles also increased dose sensitivity ten-fold relative to the parent gel formulation. This material is a suitable 3D water equivalent dosimeter with optical CT readout.

  8. Transdermal diffusion of xenon in vitro using diffusion cells

    NASA Astrophysics Data System (ADS)

    Verkhovsky, A.; Petrov, E.

    2015-11-01

    The aim of this research was to study the diffusion rate of xenon through guinea pig skin and how viscosity of cosmetic component capryl/capric triglyceride (CCT) facilitates to deliver xenon to surface of skin patches. They were placed in Franz cell for 24 hours and diffusion rate and permeability of xenon were calculated. Thus diffusion rate was 0.031 mg/hour*cm2 and permeability was 0.003 cm/hour. Using Brookfield viscometer it was shown that viscosity of CCT decreased upon increasing xenon concentration. Obtained results can be utilized in developing of new xenon containing drugs for topical administration.

  9. Millisecond Kinetics of Nanocrystal Cation Exchange UsingMicrofluidic X-ray Absorption Spectroscopy

    SciTech Connect

    Chan, Emory M.; Marcus, Matthew A.; Fakra, Sirine; Elnaggar,Mariam S.; Mathies, Richard A.; Alivisatos, A. Paul

    2007-05-07

    We describe the use of a flow-focusing microfluidic reactorto measure the kinetics of theCdSe-to-Ag2Se nanocrystal cation exchangereaction using micro-X-ray absorption spectroscopy (mu XAS). The smallmicroreactor dimensions facilitate the millisecond mixing of CdSenanocrystal and Ag+ reactant solutions, and the transposition of thereaction time onto spatial coordinates enables the in situ observation ofthe millisecond reaction with mu XAS. XAS spectra show the progression ofCdSe nanocrystals to Ag2Se over the course of 100 ms without the presenceof long-lived intermediates. These results, along with supporting stoppedflow absorption experiments, suggest that this nanocrystal cationexchange reaction is highly efficient and provide insight into how thereaction progresses in individual particles. This experiment illustratesthe value and potential of in situ microfluidic X-ray synchrotrontechniques for detailed studies of the millisecond structuraltransformations of nanoparticles and other solution-phase reactions inwhich diffusive mixing initiates changes in local bond structures oroxidation states.

  10. Arene-thioether mixed complex radical cations

    SciTech Connect

    Werst, D.W.

    1994-03-01

    Studies of radiolytically generated radical cations in aromatic hydrocarbon solvents have led to the first direct characterization of monomeric thioether radical cations in liquid solution. Observation of these very reactive chemical intermediates is made possible by the great sensitivity of fluorescence-detected magnetic resonance (FDMR) and by solvent stabilization of the thioether radical cations via electron donation. Monomeric thioether radical cations in arene solvents such as toluene exist as arene-thioether mixed complex radical cations -- the first {pi}-lone pair mixed complex radical cations ever observed. Such orbital interactions are of fundamental importance for open-shell intermediates as they have consequences for both electronic structure and reactivity. Thioether radical cations provide a valuable test system to probe the chemical influence of orbital interactions that are generic to all {pi}-type and heteroatom-containing organic radical cations, and magnetic resonance provides unsurpassed structural resolution for condensed-phase paramagnetic intermediates.

  11. The helical structure of DNA facilitates binding

    NASA Astrophysics Data System (ADS)

    Berg, Otto G.; Mahmutovic, Anel; Marklund, Emil; Elf, Johan

    2016-09-01

    The helical structure of DNA imposes constraints on the rate of diffusion-limited protein binding. Here we solve the reaction-diffusion equations for DNA-like geometries and extend with simulations when necessary. We find that the helical structure can make binding to the DNA more than twice as fast compared to a case where DNA would be reactive only along one side. We also find that this rate advantage remains when the contributions from steric constraints and rotational diffusion of the DNA-binding protein are included. Furthermore, we find that the association rate is insensitive to changes in the steric constraints on the DNA in the helix geometry, while it is much more dependent on the steric constraints on the DNA-binding protein. We conclude that the helical structure of DNA facilitates the nonspecific binding of transcription factors and structural DNA-binding proteins in general.

  12. The helical structure of DNA facilitates binding

    NASA Astrophysics Data System (ADS)

    Berg, Otto G.; Mahmutovic, Anel; Marklund, Emil; Elf, Johan

    2016-09-01

    The helical structure of DNA imposes constraints on the rate of diffusion-limited protein binding. Here we solve the reaction–diffusion equations for DNA-like geometries and extend with simulations when necessary. We find that the helical structure can make binding to the DNA more than twice as fast compared to a case where DNA would be reactive only along one side. We also find that this rate advantage remains when the contributions from steric constraints and rotational diffusion of the DNA-binding protein are included. Furthermore, we find that the association rate is insensitive to changes in the steric constraints on the DNA in the helix geometry, while it is much more dependent on the steric constraints on the DNA-binding protein. We conclude that the helical structure of DNA facilitates the nonspecific binding of transcription factors and structural DNA-binding proteins in general.

  13. 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

  14. Insights into dynamic processes of cations in pyrochlores and other complex oxides

    DOE PAGES

    Uberuaga, Blas Pedro; Perriot, Romain

    2015-08-26

    Complex oxides are critical components of many key technologies, from solid oxide fuel cells and superionics to inert matrix fuels and nuclear waste forms. In many cases, understanding mass transport is important for predicting performance and, thus, extensive effort has been devoted to understanding mass transport in these materials. However, most work has focused on the behavior of oxygen while cation transport has received relatively little attention, even though cation diffusion is responsible for many phenomena, including sintering, radiation damage evolution, and deformation processes. Here, we use accelerated molecular dynamics simulations to examine the kinetics of cation defects in onemore » class of complex oxides, A₂B₂O₇ pyrochlore. In some pyrochlore chemistries, B cation defects are kinetically unstable, transforming to A cation defects and antisites at rates faster than they can diffuse. When this occurs, transport of B cations occurs through defect processes on the A sublattice. Further, these A cation defects, either interstitials or vacancies, can interact with antisite disorder, reordering the material locally, though this process is much more efficient for interstitials than vacancies. Whether this behavior occurs in a given pyrochlore depends on the A and B chemistry. Pyrochlores with a smaller ratio of cation radii exhibit this complex behavior, while those with larger ratios exhibit direct migration of B interstitials. Similar behavior has been reported in other complex oxides such as spinels and perovskites, suggesting that this coupling of transport between the A and B cation sublattices, while not universal, occurs in many complex oxide.« less

  15. Synthesis, Structure, and Applications of α-Cationic Phosphines.

    PubMed

    Alcarazo, Manuel

    2016-09-20

    In α-cationic phosphines, at least one of the three substituents on phosphorus corresponds to a cationic (normally, but not always heteroaromatic) group, which is attached without any spacer to the phosphorus atom by a relatively inert P-C bond. This unique architecture confers to the resulting ligand strong acceptor properties, which frequently surpass those of traditional acceptor ligands such as phosphites or polyfluorinated phosphines. In addition, the fine-tuning of the stereoelectronic properties of α-cationic phosphines is also possible by judicious selection of the number and nature of the cationic groups. The opportunities offered in catalysis by α-cationic ligands arise from this ability to deplete electron density from the metals they coordinate. Thus, if in a hypothetical catalytic cycle the step that determines the rate is facilitated by an increase of the Lewis acidity at the metal center, then an acceleration of the whole process is expected by their use as ancillary ligands. Interestingly, this situation is found more frequently than one might think; many common elementary steps involved in catalytic cycles, such as reductive eliminations, coordination of substrates to metals, or attack of nucleophiles to coordinated substrates, belong to this category and are often fostered by electron poor metal centers. In this regard, our group has observed remarkable ligand acceleration effects by the employment of α-cationic phosphines in Au(I)- and Pt(II)-promoted hydroarylation and cycloisomerization reactions. These results seem to be general in π-acid catalysis when the nucleophile used is not especially electron rich because then their attack to the activated alkene or alkyne is normally rate determining. On the other hand, the use of cationic phosphines also presents drawbacks that limit their range of application. As a general rule, the reduced σ-donation from the phosphine is not compensated by the increased π-back-donation from the metal making

  16. 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.

  17. Understanding Facilitation: Theory and Principles.

    ERIC Educational Resources Information Center

    Hogan, Christine

    This book introduces newcomers to the concept of facilitation, and it presents a critical analysis of established and current theory on facilitation for existing practitioners. The following are among the topics discussed: (1) emergence of the field of facilitation; (2) development of facilitation in management; (3) development of facilitation in…

  18. Calorimetric study of cationic photopolymerization

    NASA Astrophysics Data System (ADS)

    Czajlik, I.; Hedvig, P.; Ille, A.; Dobó, J.

    1996-03-01

    The photopolymerization of penta-erythritol tetra-glycidyl ether (initiator Degacure KI-85) was studied by a du Pont 910 type DSC. From our experimental results the following conclusions can be drawn: (1) During the cationic polymerization reaction the lifetime of the initiating centers are long compared to the lifetime of free radicals in case of radical polymerization. (2) The rate of deactivation of the initiating centers increases with increasing temperature.

  19. Ti Diffusion in Zircon

    NASA Astrophysics Data System (ADS)

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

    2006-12-01

    Diffusion of Ti under anhydrous conditions at 1 atmosphere and under fluid-present conditions at 1.1-1.2 GPa has been measured in natural zircon. The source of diffusant for 1-atm experiments was a ZrO2- TiO2-ZrSiO4 mixture, with experiments run in Pt capsules. Diffusion experiments conducted in the presence of H2O-CO2 fluid were run in a piston-cylinder apparatus, using a source of ground TiO2, ZrSiO4 and SiO2, with oxalic acid added to produce H2O-CO2 vapor and partially melt the solid source material, yielding an assemblage of rutile + zircon + melt + vapor. Resonant nuclear reaction analysis (NRA) with the nuclear reaction ^{48}Ti(p,Γ)^{49}V was used to measure diffusion profiles for both sets of experiments. The following Arrhenius relation was obtained for Ti diffusion normal to c over the temperature range 1350-1550C at one atmosphere: DTi = 3.3x102 exp(-754 ± 56 kJ mol-1 /RT) m2sec-1 Ti diffusivities were found to be similar for experiments run under fluid-present conditions. A fit to all of the data yields the Arrhenius relation D = 1.3x103 exp(-741 ± 46 kJ mol-1 /RT) m2sec-1. These data suggest that zircon should be extremely retentive of Ti chemical signatures, indicating that the recently developed Ti-in-zircon crystallization geothermometer (Watson and Harrison, 2005; Watson et al., 2006) will be quite robust in preserving temperatures of zircon crystallization. Titanium diffuses somewhat faster in zircon than larger tetravalent cations U, Th, and Hf, but considerably more slowly than Pb, the REE, and oxygen; hence Ti crystallization temperatures may be retained under circumstances when radiometric ages or other types of geochemical information are lost. Watson EB, Harrison TM (2005) Science 308, 841-844. Watson EB, Wark DA, Thomas JB (2006) CMP(in press).

  20. Removal of cationic dyes by poly(acrylamide-co-acrylic acid) hydrogels in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Şolpan, Dilek; Duran, Sibel; Torun, Murat

    2008-04-01

    Poly(acrylamide-co-acrylic acid (poly(AAm-co-AAc)) hydrogels prepared by irradiating with γ-radiation were used in experiments on swelling, diffusion, and uptake of some cationic dyes such as Safranine-O (SO) and Magenta (M). Poly(AAm-co-AAc) hydrogels irradiated at 8.0 kGy have been used for swelling and diffusion studies in water and cationic dye solutions. The maximum swellings in water, and SO, and M solutions observed are 2700%, 3500%, and 4000%, respectively. Diffusions of water and cationic dyes within hydrogels have been found to be non-Fickian in character. Adsorption of the cationic dyes onto poly(AAm-co-AAc) hydrogels is studied by the batch adsorption technique. The adsorption type was found Langmuir type in the Giles classification system. The moles of adsorbed dye for SO and M per repeating unit in hydrogel (binding ratio, r) have been calculated as 3834×10 -6 and 1323×10 -6, respectively. These results show that poly(AAm-co-AAc) hydrogels can be used as adsorbent for water pollutants such as cationic dyes.

  1. Molecular crowding enhances facilitated diffusion of two human DNA glycosylases.

    PubMed

    Cravens, Shannen L; Schonhoft, Joseph D; Rowland, Meng M; Rodriguez, Alyssa A; Anderson, Breeana G; Stivers, James T

    2015-04-30

    Intracellular space is at a premium due to the high concentrations of biomolecules and is expected to have a fundamental effect on how large macromolecules move in the cell. Here, we report that crowded solutions promote intramolecular DNA translocation by two human DNA repair glycosylases. The crowding effect increases both the efficiency and average distance of DNA chain translocation by hindering escape of the enzymes to bulk solution. The increased contact time with the DNA chain provides for redundant damage patrolling within individual DNA chains at the expense of slowing the overall rate of damaged base removal from a population of molecules. The significant biological implication is that a crowded cellular environment could influence the mechanism of damage recognition as much as any property of the enzyme or DNA. PMID:25845592

  2. Vaneless diffusers

    NASA Astrophysics Data System (ADS)

    Senoo, Y.

    The influence of vaneless diffusers on flow in centrifugal compressors, particularly on surge, is discussed. A vaneless diffuser can demonstrate stable operation in a wide flow range only if it is installed with a backward leaning blade impeller. The circumferential distortion of flow in the impeller disappears quickly in the vaneless diffuser. The axial distortion of flow at the diffuser inlet does not decay easily. In large specific speed compressors, flow out of the impeller is distorted axially. Pressure recovery of diffusers at distorted inlet flow is considerably improved by half guide vanes. The best height of the vanes is a little 1/2 diffuser width. In small specific speed compressors, flow out of the impeller is not much distorted and pressure recovery can be predicted with one-dimensional flow analysis. Wall friction loss is significant in narrow diffusers. The large pressure drop at a small flow rate can cause the positive gradient of the pressure-flow rate characteristic curve, which may cause surging.

  3. Facilitative Strategies in Action.

    ERIC Educational Resources Information Center

    Fuller, Thara M. A.; Haugabrook, Adrian K.

    2001-01-01

    Describes campus-based strategies to facilitate collaboration by examining the process of restructuring a division of student affairs as an educational partner with academic affairs. Describes three collaborative efforts at the University of Massachusetts Boston: the Beacon Leadership Project, the Diversity Research Initiative, and the Beacon…

  4. The Inclusion Facilitator's Guide

    ERIC Educational Resources Information Center

    Jorgensen, Cheryl M.; Schuh, Mary C.; Nisbet, Jan

    2005-01-01

    Inclusion facilitators are educators who do more than teach children with disabilities--they advocate for change in schools and communities, sparking a passion for inclusion in teachers, administrators, and families and giving them the practical guidance they need to make it work. This is an essential new role in today's schools, and this guide…

  5. Facilitating Cognitive Development.

    ERIC Educational Resources Information Center

    Schwebel, Milton

    1985-01-01

    Human cognition research is shifting away from the importance of IQ and is emphasizing the stimulation and acceleration of a child's mental development. The emerging field of instructional psychology is trying to facilitate cognitive development. Current experimental programs--a university-school project in Belgium and a family project in…

  6. Formation of Freirian Facilitators.

    ERIC Educational Resources Information Center

    Noble, Phyllis

    This paper is written for people who are already familiar with the philosophy and methodology of Paulo Freire's liberatory education and are interested in creating a formation program for adult education facilitators using his ideas. The author describes the paper as "a collection of thoughts, of things to consider," when organizing such a…

  7. Facilitating Distance Education.

    ERIC Educational Resources Information Center

    Rossman, Mark H., Ed.; Rossman, Maxine E., Ed.

    1995-01-01

    This collection of articles on distance learning reflects the perspectives and concerns of the learner and the facilitator of learning in distance education setting. Eight chapters are included: (1) "The Evolution and Advantages of Distance Education" (John E. Cantelon) traces the history of distance education and demonstrates how it transcends…

  8. Facilitation of Adult Development

    ERIC Educational Resources Information Center

    Boydell, Tom

    2016-01-01

    Taking an autobiographical approach, I tell the story of my experiences facilitating adult development, in a polytechnic and as a management consultant. I relate these to a developmental framework of Modes of Being and Learning that I created and elaborated with colleagues. I connect this picture with a number of related models, theories,…

  9. The design of cationic lipids for gene delivery.

    PubMed

    Martin, B; Sainlos, M; Aissaoui, A; Oudrhiri, N; Hauchecorne, M; Vigneron, J-P; Lehn, J-M; Lehn, P

    2005-01-01

    Synthetic gene delivery vectors are gaining increasing importance in gene therapy as an alternative to recombinant viruses. Among the various types of non-viral vectors, cationic lipids are especially attractive as they can be prepared with relative ease and extensively characterised. Further, each of their constituent parts can be modified, thereby facilitating the elucidation of structure-activity relationships. In this forward-looking review, cationic lipid-mediated gene delivery will mainly be discussed in terms of the structure of the three basic constituent parts of any cationic lipid: the polar headgroup, hydrophobic moiety and linker. Particular emphasis will be placed on recent advances in the field as well as on our own original contributions. In addition to reviewing critical physicochemical features (such as headgroup hydration) of monovalent lipids, the use of headgroups with known nucleic-acid binding modes, such as linear and branched polyamines, aminoglycosides and guanidinium functions, will be comprehensively assessed. A particularly exciting innovation in linker design is the incorporation of environment-sensitive groups, the intracellular hydrolysis of which may lead to more controlled DNA delivery. Examples of pH-, redox- and enzyme-sensitive functional groups integrated into the linker are highlighted and the benefits of such degradable vectors can be evaluated in terms of transfection efficiency and cationic lipid-associated cytotoxicity. Finally, possible correlations between the length and type of hydrophobic moiety and transfection efficiency will be discussed. In conclusion it may be foreseen that in order to be successful, the future of cationic lipid-based gene delivery will probably require the development of sophisticated virus-like systems, which can be viewed as "programmed supramolecular systems" incorporating the various functions required to perform in a chronological order the different steps involved in gene transfection.

  10. SEARCHING FOR NAPHTHALENE CATION ABSORPTION IN THE INTERSTELLAR MEDIUM

    SciTech Connect

    Searles, Justin M.; Destree, Joshua D.; Snow, Theodore P.; Salama, Farid; York, Donald G.; Dahlstrom, Julie E-mail: destree@colorado.edu E-mail: Farid.Salama@nasa.gov E-mail: jdahlstrom1@carthage.edu

    2011-05-01

    Interstellar naphthalene cations (C{sub 10}H{sup +}{sub 8}) have been proposed by a study to be the carriers of a small number of diffuse interstellar bands (DIBs). Using an archive of high signal-to-noise spectra obtained at the Apache Point Observatory, we used two methods to test the hypothesis. Both methods failed to detect significant absorption at lab wavelengths of interstellar spectra with laboratory spectra. We thereby conclude that C{sub 10}H{sup +}{sub 8} is not a DIB carrier in typical reddened sight lines.

  11. Diffuse radiation

    NASA Technical Reports Server (NTRS)

    1981-01-01

    A diffuse celestial radiation which is isotropic at least on a course scale were measured from the soft X-ray region to about 150 MeV, at which energy the intensity falls below that of the galactic emission for most galactic latitudes. The spectral shape, the intensity, and the established degree of isotropy of this diffuse radiation already place severe constraints on the possible explanations for this radiation. Among the extragalactic theories, the more promising explanations of the isotropic diffuse emission appear to be radiation from exceptional galaxies from matter antimatter annihilation at the boundaries of superclusters of galaxies of matter and antimatter in baryon symmetric big bang models. Other possible sources for extragalactic diffuse gamma radiation are discussed and include normal galaxies, clusters of galaxies, primordial cosmic rays interacting with intergalactic matter, primordial black holes, and cosmic ray leakage from galaxies.

  12. Diffusion barriers

    NASA Technical Reports Server (NTRS)

    Nicolet, M. A.

    1983-01-01

    The choice of the metallic film for the contact to a semiconductor device is discussed. One way to try to stabilize a contact is by interposing a thin film of a material that has low diffusivity for the atoms in question. This thin film application is known as a diffusion barrier. Three types of barriers can be distinguished. The stuffed barrier derives its low atomic diffusivity to impurities that concentrate along the extended defects of a polycrystalline layer. Sacrificial barriers exploit the fact that some (elemental) thin films react in a laterally uniform and reproducible fashion. Sacrificial barriers have the advantage that the point of their failure is predictable. Passive barriers are those most closely approximating an ideal barrier. The most-studied case is that of sputtered TiN films. Stuffed barriers may be viewed as passive barriers whose low diffusivity material extends along the defects of the polycrystalline host.

  13. Cation disorder in shocked orthopyroxene.

    NASA Technical Reports Server (NTRS)

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

    1971-01-01

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

  14. Cation/Anion Associations and Transport in Ionic Polymer Membranes

    NASA Astrophysics Data System (ADS)

    Madsen, Louis; Hou, Jianbo; Zhang, Zhiyang; Li, Jing

    2011-03-01

    Ionic polymer membranes and ionic liquids (ILs) find fruitful applications in a range of ion conduction applications, from electromechanical ``artificial muscles'' to organic batteries. Various intermolecular interactions determine local structure and dynamics in these ion-dense media. In particular, ion aggregation can drastically affect ion transport, especially since neutral species (dipoles, quadrupoles...) will not be driven by electric fields. We are investigating mixtures of different ILs, ILs with water, and ILs swollen into ionomer membranes, using pulsed-gradient NMR to probe diffusion and electrophoretic mobility. We observe strong dependencies of the cation/anion diffusion coefficient ratio (ranging from 3X to 0.25X) on mixture and membrane properties, which we relate to ion association phenomena. We will further discuss NMR for transport and dynamics studies, especially regarding chemically resolved transport of various mobile species, probing a range of length and time scales, and quantifying ion aggregation.

  15. Amplitude equations for reaction-diffusion systems with cross diffusion

    NASA Astrophysics Data System (ADS)

    Zemskov, Evgeny P.; Vanag, Vladimir K.; Epstein, Irving R.

    2011-09-01

    Using Taylor series expansion, multiscaling, and further expansion in powers of a small parameter, we develop general amplitude equations for two-variable reaction-diffusion systems with cross-diffusion terms in the cases of Hopf and Turing instabilities. We apply this analysis to the Oregonator and Brusselator models and find that inhibitor cross diffusion induced by the activator and activator cross diffusion induced by the inhibitor have opposite effects in the two models as a result of the different structure of their community matrices. Our analysis facilitates finding regions of supercritical and subcritical bifurcations, as well as wave and antiwave domains and domains of turbulent waves in the case of Hopf instability.

  16. Amplitude equations for reaction-diffusion systems with cross diffusion.

    PubMed

    Zemskov, Evgeny P; Vanag, Vladimir K; Epstein, Irving R

    2011-09-01

    Using Taylor series expansion, multiscaling, and further expansion in powers of a small parameter, we develop general amplitude equations for two-variable reaction-diffusion systems with cross-diffusion terms in the cases of Hopf and Turing instabilities. We apply this analysis to the Oregonator and Brusselator models and find that inhibitor cross diffusion induced by the activator and activator cross diffusion induced by the inhibitor have opposite effects in the two models as a result of the different structure of their community matrices. Our analysis facilitates finding regions of supercritical and subcritical bifurcations, as well as wave and antiwave domains and domains of turbulent waves in the case of Hopf instability. PMID:22060484

  17. Facilitation as a teaching strategy : experiences of facilitators.

    PubMed

    Lekalakala-Mokgele, E

    2006-08-01

    Changes in nursing education involve the move from traditional teaching approaches that are teacher-centred to facilitation, a student centred approach. The student-centred approach is based on a philosophy of teaching and learning that puts the learner on centre-stage. The aim of this study was to identify the challenges of facilitators of learning using facilitation as a teaching method and recommend strategies for their (facilitators) development and support. A qualitative, explorative and contextual design was used. Four (4) universities in South Africa which utilize facilitation as a teaching/ learning process were identified and the facilitators were selected to be the sample of the study. The main question posed during in-depth group interviews was: How do you experience facilitation as a teaching/learning method?. Facilitators indicated different experiences and emotions when they first had to facilitate learning. All of them indicated that it was difficult to facilitate at the beginning as they were trained to lecture and that no format for facilitation was available. They experienced frustrations and anxieties as a result. The lack of knowledge of facilitation instilled fear in them. However they indicated that facilitation had many benefits for them and for the students. Amongst the ones mentioned were personal and professional growth. Challenges mentioned were the fear that they waste time and that they do not cover the content. It is therefore important that facilitation be included in the training of nurse educators. PMID:17131610

  18. Metal cation controls myosin and actomyosin kinetics

    PubMed Central

    Tkachev, Yaroslav V; Ge, Jinghua; Negrashov, Igor V; Nesmelov, Yuri E

    2013-01-01

    We have perturbed myosin nucleotide binding site with magnesium-, manganese-, or calcium-nucleotide complexes, using metal cation as a probe to examine the pathways of myosin ATPase in the presence of actin. We have used transient time-resolved FRET, myosin intrinsic fluorescence, fluorescence of pyrene labeled actin, combined with the steady state myosin ATPase activity measurements of previously characterized D.discoideum myosin construct A639C:K498C. We found that actin activation of myosin ATPase does not depend on metal cation, regardless of the cation-specific kinetics of nucleotide binding and dissociation. The rate limiting step of myosin ATPase depends on the metal cation. The rate of the recovery stroke and the reverse recovery stroke is directly proportional to the ionic radius of the cation. The rate of nucleotide release from myosin and actomyosin, and ATP binding to actomyosin depends on the cation coordination number. PMID:24115140

  19. ADSORPTION METHOD FOR SEPARATING METAL CATIONS

    DOEpatents

    Khym, J.X.

    1959-03-10

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

  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. Evaluation of factors affecting diffusion in compacted bentonite

    SciTech Connect

    Lehikoinen, J.; Carlsson, T.; Muurinen, A.; Olin, M.; Salonen, P.

    1996-08-01

    The information available from the open literature and studies on exclusion, sorption and diffusion mechanisms of ionic and neutral species in bentonite has been compiled and re-examined in relation to the microstructure of bentonite. The emphasis is placed on a more thorough understanding of the diffusion processes taking place in compacted bentonite. Despite the scarcity of experiments performed with neutral diffusants, these imply that virtually all the pores in compacted bentonite are accessible to neutral species. Anion exclusion, induced by the overlap of electrical double layers, may render the accessible porosity for anions considerably less than the porosity obtained from the water content of the clay. On the basis of the compiled data, it is highly probable that surface diffusion plays a significant role in the transport of cations in bentonite clays. Moreover, easily soluble compounds in bentonite can affect the ionic strength of porewater and, consequently, exclusion, equilibrium between cations, and surface diffusion.

  2. Demonstrating Diffusion

    ERIC Educational Resources Information Center

    Foy, Barry G.

    1977-01-01

    Two demonstrations are described. Materials and instructions for demonstrating movement of molecules into cytoplasm using agar blocks, phenolphthalein, and sodium hydroxide are given. A simple method for demonstrating that the rate of diffusion of a gas is inversely proportional to its molecular weight is also presented. (AJ)

  3. Relativistic diffusion

    NASA Astrophysics Data System (ADS)

    Haba, Z.

    2009-02-01

    We discuss relativistic diffusion in proper time in the approach of Schay (Ph.D. thesis, Princeton University, Princeton, NJ, 1961) and Dudley [Ark. Mat. 6, 241 (1965)]. We derive (Langevin) stochastic differential equations in various coordinates. We show that in some coordinates the stochastic differential equations become linear. We obtain momentum probability distribution in an explicit form. We discuss a relativistic particle diffusing in an external electromagnetic field. We solve the Langevin equations in the case of parallel electric and magnetic fields. We derive a kinetic equation for the evolution of the probability distribution. We discuss drag terms leading to an equilibrium distribution. The relativistic analog of the Ornstein-Uhlenbeck process is not unique. We show that if the drag comes from a diffusion approximation to the master equation then its form is strongly restricted. The drag leading to the Tsallis equilibrium distribution satisfies this restriction whereas the one of the Jüttner distribution does not. We show that any function of the relativistic energy can be the equilibrium distribution for a particle in a static electric field. A preliminary study of the time evolution with friction is presented. It is shown that the problem is equivalent to quantum mechanics of a particle moving on a hyperboloid with a potential determined by the drag. A relation to diffusions appearing in heavy ion collisions is briefly discussed.

  4. Defusing Diffusion

    ERIC Educational Resources Information Center

    Dou, Remy; Hogan, DaNel; Kossover, Mark; Spuck, Timothy; Young, Sarah

    2013-01-01

    Diffusion has often been taught in science courses as one of the primary ways by which molecules travel, particularly within organisms. For years, classroom teachers have used the same common demonstrations to illustrate this concept (e.g., placing drops of food coloring in a beaker of water). Most of the time, the main contributor to the motion…

  5. Relativistic diffusion.

    PubMed

    Haba, Z

    2009-02-01

    We discuss relativistic diffusion in proper time in the approach of Schay (Ph.D. thesis, Princeton University, Princeton, NJ, 1961) and Dudley [Ark. Mat. 6, 241 (1965)]. We derive (Langevin) stochastic differential equations in various coordinates. We show that in some coordinates the stochastic differential equations become linear. We obtain momentum probability distribution in an explicit form. We discuss a relativistic particle diffusing in an external electromagnetic field. We solve the Langevin equations in the case of parallel electric and magnetic fields. We derive a kinetic equation for the evolution of the probability distribution. We discuss drag terms leading to an equilibrium distribution. The relativistic analog of the Ornstein-Uhlenbeck process is not unique. We show that if the drag comes from a diffusion approximation to the master equation then its form is strongly restricted. The drag leading to the Tsallis equilibrium distribution satisfies this restriction whereas the one of the Jüttner distribution does not. We show that any function of the relativistic energy can be the equilibrium distribution for a particle in a static electric field. A preliminary study of the time evolution with friction is presented. It is shown that the problem is equivalent to quantum mechanics of a particle moving on a hyperboloid with a potential determined by the drag. A relation to diffusions appearing in heavy ion collisions is briefly discussed.

  6. 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

  7. 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.

  8. 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.

  9. Mathematical Modeling of Cation Contamination in a Proton-exchange Membrane

    SciTech Connect

    Weber, Adam; Delacourt, Charles

    2008-09-11

    Transport phenomena in an ion-exchange membrane containing both H+ and K+ are described using multicomponent diffusion equations (Stefan-Maxwell). A model is developed for transport through a Nafion 112 membrane in a hydrogen-pump setup. The model results are analyzed to quantify the impact of cation contamination on cell potential. It is shown that limiting current densities can result due to a decrease in proton concentration caused by the build-up of contaminant ions. An average cation concentration of 30 to 40 percent is required for appreciable effects to be noticed under typical steady-state operating conditions.

  10. 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.

  11. Cation exchange capacity of pine bark substrates

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Cation exchange capacity (CEC) is an important soil and substrate chemical property. It describes a substrate's ability to retain cation nutrients. Higher CEC values for a substrate generally result in greater amounts of nutrients retained in the substrate and available for plant uptake, and great...

  12. 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.

  13. 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.

  14. Diffusion bonding

    DOEpatents

    Anderson, Robert C.

    1976-06-22

    1. A method for joining beryllium to beryllium by diffusion bonding, comprising the steps of coating at least one surface portion of at least two beryllium pieces with nickel, positioning a coated surface portion in a contiguous relationship with an other surface portion, subjecting the contiguously disposed surface portions to an environment having an atmosphere at a pressure lower than ambient pressure, applying a force upon the beryllium pieces for causing the contiguous surface portions to abut against each other, heating the contiguous surface portions to a maximum temperature less than the melting temperature of the beryllium, substantially uniformly decreasing the applied force while increasing the temperature after attaining a temperature substantially above room temperature, and maintaining a portion of the applied force at a temperature corresponding to about maximum temperature for a duration sufficient to effect the diffusion bond between the contiguous surface portions.

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

    PubMed Central

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

    2016-01-01

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

  16. Why Does the Intestine Lack Basolateral Efflux Transporters for Cationic Compounds? A Provocative Hypothesis.

    PubMed

    Proctor, William R; Ming, Xin; Bourdet, David; Han, Tianxiang Kevin; Everett, Ruth S; Thakker, Dhiren R

    2016-02-01

    Transport proteins in intestinal epithelial cells facilitate absorption of nutrients/compounds that are organic anions, cations, and zwitterions. For two decades, we have studied intestinal absorption and transport of hydrophilic ionic compounds, with specific focus on transport properties of organic cations and their interactions with intestinal transporters and tight junction proteins. Our data reveal how complex interactions between a compound and transporters in intestinal apical/basolateral (BL) membranes and tight junction proteins define oral absorption, and that the BL membrane lacks an efflux transporter that can transport positively charged compounds. Based on our investigations of transport mechanisms of zwitterionic, anionic, and cationic compounds, we postulate that physicochemical properties of these ionic species, in relation to the intestinal micro pH environment, have exerted evolutionary pressure for development of transporters that can handle apical uptake/efflux of all 3 ionic species and BL efflux of anions and zwitterions, but such evolutionary pressure is lacking for development of a BL efflux transporter for cationic compounds. This review provides an overview of intestinal uptake/efflux transporters and describes our studies on intestinal transport of cationic, anionic, and zwitterionic drugs that led to hypothesize that there are no cation-selective BL efflux transporters in the intestine. PMID:26869413

  17. Effect of tetraalkylammonium cations on gas coalescence at a hydrogen-evolving microelectrode.

    PubMed

    Monzon, Lorena M A; Gillen, Alice J; Mobius, Matthias E; Coey, J M D

    2015-06-01

    Hydrogen gas evolution at the surface of a microelectrode may result in periodic release of single bubbles larger than the electrode diameter. Bubbles often grow by incorporating smaller bubbles that coalesce with them. To explore the coalescence, we investigate how a series of six tetralkylammonium cations (TXA(+)), where the number of carbons on the alkyl chain varies from 1 to 6, affects the oscillatory behavior of the gas-evolving microcathode. Different concentrations of TXA(+) bromide salts ranging from a few micromolar up to 1 M were added in the acid electrolyte. The frequency of bubble release and the transition from periodic to aperiodic release are related to the inhibition of bubble coalescence and gas streaming. The concentration range where this transition occurs depends strongly on the cation hydrophobicity and it ranges from very small values for the hydrophobic cations to over 1 M for the most hydrophilic one. For some of the TXA(+) cations, the transition shows a smooth increase in release frequency before switching completely to bubble-stream behavior, while for others the transition is abrupt. A smooth increase in the gas oscillator frequency with concentration indicates that the adsorption of TXA(+) cations on the bubble surface is mass transport-limited. The inhibition of bubble coalescence by the smallest cations is electrochemically driven, facilitated by specific interactions established between the ions and the electrode surface. PMID:25970227

  18. Facilitating post traumatic growth

    PubMed Central

    Turner, de Sales; Cox, Helen

    2004-01-01

    Background Whilst negative responses to traumatic injury have been well documented in the literature, there is a small but growing body of work that identifies posttraumatic growth as a salient feature of this experience. We contribute to this discourse by reporting on the experiences of 13 individuals who were traumatically injured, had undergone extensive rehabilitation and were discharged from formal care. All participants were injured through involvement in a motor vehicle accident, with the exception of one, who was injured through falling off the roof of a house. Methods In this qualitative study, we used an audio-taped in-depth interview with each participant as the means of data collection. Interviews were transcribed verbatim and analysed thematically to determine the participants' unique perspectives on the experience of recovery from traumatic injury. In reporting the findings, all participants' were given a pseudonym to assure their anonymity. Results Most participants indicated that their involvement in a traumatic occurrence was a springboard for growth that enabled them to develop new perspectives on life and living. Conclusion There are a number of contributions that health providers may make to the recovery of individuals who have been traumatically injured to assist them to develop new views of vulnerability and strength, make changes in relationships, and facilitate philosophical, physical and spiritual growth. PMID:15248894

  19. Implications of cation exchange on clay release and colloid-facilitated transport in porous media

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Column experiments were conducted to study chemical factors that influence the release of clay (kaolinite and quartz minerals) from saturated Ottawa sand of different sizes (710, 360, and 240 µm). A relatively minor enhancement of clay release occurred when the pH was increased (5.8 to 10) or the i...

  20. Intracellular trafficking mechanism of cationic phospholipids including cationic liposomes in HeLa cells.

    PubMed

    Un, K; Sakai-Kato, K; Goda, Y

    2014-07-01

    The development of gene delivery methods is essential for the achievement of effective gene therapy. Elucidation of the intracellular transfer mechanism for cationic carriers is in progress, but there are few reports regarding the intracellular trafficking processes of the cationic phospholipids taken up into cells. In the present work, the trafficking processes of a cationic phospholipid (1,2-dioleoyl-3-trimethylammonium-propane, DOTAP) were investigated from intracellular uptake to extracellular efflux using cationic liposomes in vitro. Following intracellular transport of liposomes via endocytosis, DOTAP was localized in the endoplasmic reticulum, Golgi apparatus, and mitochondria. Moreover, the proteins involved in DOTAP intracellular trafficking and extracellular efflux were identified. In addition, helper lipids of cationic liposomes were found to partially affect this intracellulartrafficking. These findings might provide valuable information for designing cationic carriers and avoiding unexpected toxic side effects derived from cationic liposomal components.

  1. Memory facilitation educed by food intake.

    PubMed

    Oomura, Y; Sasaki, K; Li, A J

    1993-09-01

    Acidic fibroblast growth factor (aFGF) in rat CSF increased 1000 times in the 2-h period after food intake, or IP, or ICV glucose infusion. The ICV application of aFGF dose dependently depresses and anti-aFGF antibody facilitates food intake. aFGF is produced in the ependymal cells and released into the CSF in response to increased glucose in the CSF caused by food intake. Released aFGF diffused into the brain parenchyma and was taken up into neurons in the hypothalamus, hippocampus, amygdala, etc. IP injection of glucose 2 h before a task that combined acquisition with passive avoidance significantly increased retention of avoidance by mice tested 24 h later. In a Morris water maze task, IP glucose injection 2 h before a first trial block reduced time to find and climb onto a platform hidden just below the water surface. The glucose facilitation of these affective and spatial memory were abolished by pretreatment with anti-aFGF antibody applied ICV. Continuous ICV infusion of aFGF into rats also significantly increased the reliability of passive avoidance for several days. After food intake, centrally released aFGF reaches the hippocampus and facilitates memory; peripherally released cholecystokinin reaches the endings of the afferent vagal nerves in the portal vein and changes their activity, which modulates hippocampal activity, to lead to memory facilitation. This, however, is blocked by vagotomy below the diaphragm. The results indicate the importance of food intake, not only to maintain homeostasis, but also to prepare a readiness state for memory facilitation. PMID:7692459

  2. Kinetic and chemical mechanisms for the effects of univalent cations on the spectral properties of aromatic amine dehydrogenase.

    PubMed Central

    Zhu, Z; Davidson, V L

    1998-01-01

    Univalent cations and pH influence the UV-visible absorption spectrum of the tryptophan tryptophylquinone (TTQ) enzyme, aromatic amine dehydrogenase (AADH). Little spectral perturbation was observed when pH was varied in the absence of univalent cations. The addition of alkali metal univalent cations (K+, Na+, Li+, Rb+ or Cs+) to oxidized AADH caused significant changes in its absorption spectrum. The apparent Kd for each cation, determined from titrations of the spectral perturbation, decreased with increasing pH. Transient kinetic studies involving rapid mixing of AADH with cations and pH jump revealed that the rate of the cation-induced spectral changes initially decreased with increasing cation concentration to a minimum value, then increased with increasing cation concentration. A kinetic model was developed to fit these data, determine the true pH-independent Kd values for K+ and Na+, and explain the pH-dependence of the apparent Kd. A chemical reaction mechanism, based on the kinetic data, is presented in which the metallic univalent cation facilitates the chemical modification of the TTQ prosthetic group to form an hydroxide adduct which gives rise to the spectral change. Addition of NH4(+)/NH3 to AADH caused changes in the absorption spectrum which were very different form those caused by addition of the metallic univalent cations. The kinetics of the reaction induced by addition of NH4+/NH3 were also different, being simple saturation kinetics. Another reaction mechanism is proposed for the NH4+/NH3-induced spectral change that involves nucleophilic addition of the unprotonated NH3 to TTQ. The general relevance of these data and models to the physiological reactions of TTQ-dependent enzymes and to the roles of univalent cations in modulating enzyme activity are discussed. PMID:9405291

  3. Diffusion in Brain Extracellular Space

    PubMed Central

    Syková, Eva; Nicholson, Charles

    2009-01-01

    Diffusion in the extracellular space (ECS) of the brain is constrained by the volume fraction and the tortuosity and a modified diffusion equation represents the transport behavior of many molecules in the brain. Deviations from the equation reveal loss of molecules across the blood-brain barrier, through cellular uptake, binding or other mechanisms. Early diffusion measurements used radiolabeled sucrose and other tracers. Presently, the real-time iontophoresis (RTI) method is employed for small ions and the integrative optical imaging (IOI) method for fluorescent macromolecules, including dextrans or proteins. Theoretical models and simulations of the ECS have explored the influence of ECS geometry, effects of dead-space microdomains, extracellular matrix and interaction of macromolecules with ECS channels. Extensive experimental studies with the RTI method employing the cation tetramethylammonium (TMA) in normal brain tissue show that the volume fraction of the ECS typically is about 20% and the tortuosity about 1.6 (i.e. free diffusion coefficient of TMA is reduced by 2.6), although there are regional variations. These parameters change during development and aging. Diffusion properties have been characterized in several interventions, including brain stimulation, osmotic challenge and knockout of extracellular matrix components. Measurements have also been made during ischemia, in models of Alzheimer's and Parkinson's diseases and in human gliomas. Overall, these studies improve our conception of ECS structure and the roles of glia and extracellular matrix in modulating the ECS microenvironment. Knowledge of ECS diffusion properties are valuable in contexts ranging from understanding extrasynaptic volume transmission to the development of paradigms for drug delivery to the brain. PMID:18923183

  4. 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.

  5. Synthesis, structure determination, and infrared spectroscopy of (NpO{sub 2}){sub 2}(SO{sub 4})(H{sub 2}O){sub 4}: Prevalence of cation-cation interactions and cationic nets in neptunyl sulfate compounds

    SciTech Connect

    Forbes, T.Z. Burns, P.C.

    2009-01-15

    The compound (NpO{sub 2}){sub 2}(SO{sub 4})(H{sub 2}O){sub 4} was synthesized by evaporation of a Np{sup 5+} sulfate solution. The crystal structure was determined using single crystal X-ray diffraction and refined to an R{sub 1}=0.0310. (NpO{sub 2}){sub 2}(SO{sub 4})(H{sub 2}O){sub 4} crystallizes in triclinic space group P-1, a=8.1102(7) A, b=8.7506(7) A, c=16.234(1) A, {alpha}=90.242(2){sup o}, {beta}=92.855(2){sup o}, {gamma}=113.067(2){sup o}, V=1058.3(2) A{sup 3}, and Z=2. The structure contains neptunyl pentagonal bipyramids that share vertices through cation-cation interactions to form a sheet or cationic net. The sheet is decorated on each side by vertex sharing with sulfate tetrahedra, and adjacent sheets are linked together through hydrogen bonding. A graphical representation of (NpO{sub 2}){sub 2}(SO{sub 4})(H{sub 2}O){sub 4} was constructed to facilitate the structural comparison to similar Np{sup 5+} compounds. The prevalence of the cationic nets in neptunyl sulfate compounds related to the overall stability of the structure is also discussed. - Graphical abstract: (NpO{sub 2}){sub 2}(SO{sub 4})(H{sub 2}O){sub 4} was synthesized by hydrothermal methods and its structure determined. A graphical representation of the compound was constructed to facilitate the structural comparison to similar Np{sup 5+} compounds and the prevalence of the cationic nets in neptunyl sulfate compounds related to the overall stability of the structure is discussed.

  6. Cationic phospholipids: structure transfection activity relationships

    SciTech Connect

    Koynova, Rumiana; Tenchov, Boris

    2010-01-18

    Synthetic cationic lipids are presently the most widely used non-viral gene carriers. Examined here is a particularly attractive cationic lipid class, triester phosphatidylcholines (PCs) exhibiting low toxicities and good transfection efficiency. Similarly to other cationic lipids, they form stable complexes (lipoplexes) with the polyanionic nucleic acids. A summary of studies on a set of {approx}30 cationic PCs reveals the existence of a strong, systematic dependence of their transfection efficiency on the lipid hydrocarbon chain structure: transfection activity increases with increase of chain unsaturation from 0 to 2 double bonds per lipid and decreases with increase of chain length in the range {approx}30-50 total number of chain carbon atoms. Maximum transfection was observed for ethyl phosphate PCs (EPCs) with monounsaturated 14:1 chains (total of 2 double bonds and 30 chain carbon atoms). Lipid phase behavior is known to depend strongly on the chain molecular structure and the above relationships thus substantiate a view that cationic PC phase propensities are an important determinant of their activity. Indeed, X-ray structural studies show that the rate of DNA release from lipoplexes as well as transfection activity well correlate with non-lamellar phase progressions observed in cationic PC mixtures with membrane lipids. These findings appear to be of considerable interest because, according to current views, key processes in lipid-mediated transfection such as lipoplex disassembly and DNA release within the cells are believed to take place upon cationic lipid mixing with cellular lipids.

  7. DIFFUSION PUMP

    DOEpatents

    Levenson, L.

    1963-09-01

    A high-vacuum diffusion pump is described, featuring a novel housing geometry for enhancing pumping speed. An upright, cylindrical lower housing portion is surmounted by a concentric, upright, cylindrical upper housing portion of substantially larger diameter; an uppermost nozzle, disposed concentrically within the upper portion, is adapted to eject downwardly a conical sheet of liquid outwardly to impinge upon the uppermost extremity of the interior wall of the lower portion. Preferably this nozzle is mounted upon a pedestal rising coaxially from within the lower portion and projecting up into said upper portion. (AEC)

  8. 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.

  9. 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

  10. Penetration and lateral diffusion characteristics of polycrystalline graphene barriers.

    PubMed

    Yoon, Taeshik; Mun, Jeong Hun; Cho, Byung Jin; Kim, Taek-Soo

    2014-01-01

    We report penetration and lateral diffusion behavior of environmental molecules on synthesized polycrystalline graphene. Penetration occurs through graphene grain boundaries resulting in local oxidation. However, when the penetrated molecules diffuse laterally, the oxidation region will expand. Therefore, we measured the lateral diffusion rate along the graphene-copper interface for the first time by the environment-assisted crack growth test. It is clearly shown that the lateral diffusion is suppressed due to the high van der Waals interaction. Finally, we employed bilayer graphene for a perfect diffusion barrier facilitated by decreased defect density and increased lateral diffusion path.

  11. Structural Insights into Divalent Cation Modulations of ATP-Gated P2X Receptor Channels.

    PubMed

    Kasuya, Go; Fujiwara, Yuichiro; Takemoto, Mizuki; Dohmae, Naoshi; Nakada-Nakura, Yoshiko; Ishitani, Ryuichiro; Hattori, Motoyuki; Nureki, Osamu

    2016-02-01

    P2X receptors are trimeric ATP-gated cation channels involved in physiological processes ranging widely from neurotransmission to pain and taste signal transduction. The modulation of the channel gating, including that by divalent cations, contributes to these diverse physiological functions of P2X receptors. Here, we report the crystal structure of an invertebrate P2X receptor from the Gulf Coast tick Amblyomma maculatum in the presence of ATP and Zn(2+) ion, together with electrophysiological and computational analyses. The structure revealed two distinct metal binding sites, M1 and M2, in the extracellular region. The M1 site, located at the trimer interface, is responsible for Zn(2+) potentiation by facilitating the structural change of the extracellular domain for pore opening. In contrast, the M2 site, coupled with the ATP binding site, might contribute to regulation by Mg(2+). Overall, our work provides structural insights into the divalent cation modulations of P2X receptors. PMID:26804916

  12. Adsorption of monovalent cations to bilayer membranes containing negative phospholipids.

    PubMed

    Eisenberg, M; Gresalfi, T; Riccio, T; McLaughlin, S

    1979-11-13

    The electrophoretic mobilities of multilamellar phosphatidylserine vesicles were measured in solutions containing monovalent cations, and the xi potentials, the electrostatic potentials at the hydrodynamic plane of shear, were calculated from the Helmholtz--Smoluchowski equation. In the presence of 0.1 M lithium, sodium, ammonium, potassium, rubidium, cesium, tetraethylammonium, and tetramethylammonium chloride, the xi potentials were -60, -62, -72, -73, -77, -80, -82, and -91 mV, respectively. Similar results were obtained with phosphatidylglycerol vesicles; different results were obtained with cardiolipin, phosphatidylinositol, and phosphatidic acid vesicles. The phosphatidylserine results are interpreted in terms of the Stern equation, a combination of the Gouy equation from the theory of the diffuse double layer, the Boltzmann relation, and the Langmuir adsorption isotherm. Evidence is presented that suggests the hydrodynamic plane of shear is 2 A from the surface of the membrane in solutions containing the alkali metal cations. With this assumption, the intrinsic association constants of the above monovalent cations with phosphatidylserine are 0.8, 0.6, 0.17, 0.15, 0.08, 0.05, 0.03, and 0 M-1, respectively. The validity of this approach was tested in two ways. First, the xi potentials of vesicles formed from mixtures of phosphatidylserine and a zwitterionic lipid, phosphatidylcholine, were measured in solutions containing different concentrations of sodium. All the data could be described by the Stern equation if the "relaxation" of the ionic atmosphere, which is predicted by classic electrostatic and hydrodynamic theory to occur at low salt concentrations and high potentials, was circumvented by using only large (diameter greater than 13 micrometers) vesicles for these measurements. Second, the fluorescent probe 2-(p-toluidinyl)naphthalene-6-sulfonate was used to estimate the potential at the surface of phosphatidylserine and phosphatidylglycerol vesicles

  13. Characterization of carrageenan hydrogel electrode coatings with immobilized cationic metal complex redox couples

    SciTech Connect

    Crumbliss, A.L.; Perine, S.C.; Edwards, A.K.; Rillema, D.P.

    1992-02-06

    The redox behavior of cationic metal complexes immobilized in a {kappa}-carrageenan hydrogel matrix, which acts as a cation-exchange polymeric electrode coating, is described. Ru(bpy){sub 3}{sup 2+}, Ru(en){sub 3}{sup 3+}, Ru(NH{sub 3}){sub 6}{sup 3+}, and Co(bpy){sub 3}{sup 3+} (bpy = 2,2{prime}-bipyridine; en = ethylenediamine) were immobilized singly and in pairs (Ru(bpy){sub 3}{sup 2+} and Co (bpy){sub 3}{sup 3+}) on the surface of a Pt electrode and were characterized by cyclic voltammetry. The redox couples were selected on the basis of their structural similarity and wide range of electron self-exchange rate constants (10{sup 1}-10{sup 9} M{sup -1} s{sup -1}). The surface-modified carrageenan hydrogel electrode was found to exhibit superior electrolyte diffusion properties when compared with more commonly used cation-exchange immobilization matrices such as Nafion, and to be stable with respect to leakage of cations into the solution. The carrageenan hydrogel film was also found to be permeable to anionic redox couples such as Fe(CN){sub 6}{sup 3-/4-}. All immobilized redox couples exhibited quasi-reversible electrochemical behavior. Evidence supporting a dual-mode mechanism involving physical diffusion and electron hopping for charge propagation through the carrageenan hydrogel is presented. 45 refs., 2 figs., 4 tabs.

  14. Cationic ruthenium alkylidene catalysts bearing phosphine ligands.

    PubMed

    Endo, Koji; Grubbs, Robert H

    2016-02-28

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

  15. 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.

  16. Cationic Polyene Phospholipids as DNA Carriers for Ocular Gene Therapy

    PubMed Central

    Machado, Susana; Calado, Sofia; Bitoque, Diogo; Oliveira, Ana Vanessa; Øpstad, Christer L.; Zeeshan, Muhammad; Sliwka, Hans-Richard; Partali, Vassilia; Pungente, Michael D.; Silva, Gabriela A.

    2014-01-01

    Recent success in the treatment of congenital blindness demonstrates the potential of ocular gene therapy as a therapeutic approach. The eye is a good target due to its small size, minimal diffusion of therapeutic agent to the systemic circulation, and low immune and inflammatory responses. Currently, most approaches are based on viral vectors, but efforts continue towards the synthesis and evaluation of new nonviral carriers to improve nucleic acid delivery. Our objective is to evaluate the efficiency of novel cationic retinoic and carotenoic glycol phospholipids, designated C20-18, C20-20, and C30-20, to deliver DNA to human retinal pigmented epithelium (RPE) cells. Liposomes were produced by solvent evaporation of ethanolic mixtures of the polyene compounds and coformulated with 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE) or cholesterol (Chol). Addition of DNA to the liposomes formed lipoplexes, which were characterized for binding, size, biocompatibility, and transgene efficiency. Lipoplex formulations of suitable size and biocompatibility were assayed for DNA delivery, both qualitatively and quantitatively, using RPE cells and a GFP-encoding plasmid. The retinoic lipoplex formulation with DOPE revealed a transfection efficiency comparable to the known lipid references 3β-[N-(N′,N′-dimethylaminoethane)-carbamoyl]-cholesterol (DC-Chol) and 1,2-dioleoyl-sn-glycero-3-ethylphosphocholine (EPC) and GeneJuice. The results demonstrate that cationic polyene phospholipids have potential as DNA carriers for ocular gene therapy. PMID:25147812

  17. Effects of cation concentration on photocatalytic performance over magnesium vanadates

    NASA Astrophysics Data System (ADS)

    Li, Peng; Zhou, Wei; Wang, Xin; Zhang, Yan; Umezawa, Naoto; Abe, Hideki; Ye, Jinhua; Wang, Defa

    2015-10-01

    A series of magnesium vanadates (MgV 2O6, Mg2V 2O7, and Mg3V 2O8) were synthesized to investigate the effect of cation concentration on photocatalytic performance. The samples were characterized by X-ray diffraction, field emission-scanning electron microscopy, UV-visible diffuse reflectance spectroscopy, and fluorescence spectroscopy. The photocatalytic O2 evolution experiments under visible light irradiation showed Mg2V 2O7 exhibits the best performance, while Mg3V 2O8 has the lowest activity. The density functional theory calculations indicated that the lowest unoccupied states of Mg3V 2O8 are the mostly localized by the cation layers. The fluorescence spectra and fluorescence decay curves gave evident performances of excited states of magnesium vanadates and pointed out MgV 2O6 has a very short excited electron lift-time. Mg2V 2O7 performs high photocatalytic activity because of its high electron mobility and long electron life-time.

  18. Effects of cation concentration on photocatalytic performance over magnesium vanadates

    SciTech Connect

    Li, Peng; Zhou, Wei; Wang, Xin; Zhang, Yan; Wang, Defa; Umezawa, Naoto E-mail: ABE.Hideki@nims.go.jp; Abe, Hideki E-mail: ABE.Hideki@nims.go.jp; Ye, Jinhua

    2015-10-01

    A series of magnesium vanadates (MgV {sub 2}O{sub 6}, Mg{sub 2}V {sub 2}O{sub 7}, and Mg{sub 3}V {sub 2}O{sub 8}) were synthesized to investigate the effect of cation concentration on photocatalytic performance. The samples were characterized by X-ray diffraction, field emission-scanning electron microscopy, UV-visible diffuse reflectance spectroscopy, and fluorescence spectroscopy. The photocatalytic O{sub 2} evolution experiments under visible light irradiation showed Mg{sub 2}V {sub 2}O{sub 7} exhibits the best performance, while Mg{sub 3}V {sub 2}O{sub 8} has the lowest activity. The density functional theory calculations indicated that the lowest unoccupied states of Mg{sub 3}V {sub 2}O{sub 8} are the mostly localized by the cation layers. The fluorescence spectra and fluorescence decay curves gave evident performances of excited states of magnesium vanadates and pointed out MgV {sub 2}O{sub 6} has a very short excited electron lift-time. Mg{sub 2}V {sub 2}O{sub 7} performs high photocatalytic activity because of its high electron mobility and long electron life-time.

  19. 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.

  20. 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.

  1. Quasielastic neutron scattering studies on glass-forming ionic liquids with imidazolium cations

    SciTech Connect

    Kofu, Maiko; Inamura, Yasuhiro; Miyazaki, Kyoko; Yamamuro, Osamu; Tyagi, Madhusudan

    2015-12-21

    Relaxation processes for imidazolium-based ionic liquids (ILs) were investigated by means of an incoherent quasielastic neutron scattering technique. In order to clarify the cation and anion effects on the relaxation processes, ten samples were measured. For all of the samples, we found three relaxations at around 1 ps, 10 ps, and 100 ps-10 ns, each corresponding to the alkyl reorientation, the relaxation related to the imidazolium ring, and the ionic diffusion. The activation energy (E{sub a}) for the alkyl relaxation is insensitive to both anion and alkyl chain lengths. On the other hand, for the imidazolium relaxation and the ionic diffusion processes, E{sub a} increases as the anion size decreases but is almost independent of the alkyl chain length. This indicates that the ionic diffusion and imidazolium relaxation are governed by the Coulombic interaction between the core parts of the cations (imidazolium ring) and the anions. This is consistent with the fact that the imidazolium-based ILs have nanometer scale structures consisting of ionic and neutral (alkyl chain) domains. It is also found that there is a clear correlation between the ionic diffusion and viscosity, indicating that the ionic diffusion is mainly associated with the glass transition which is one of the characteristics of imidazolium-based ILs.

  2. Quasielastic neutron scattering studies on glass-forming ionic liquids with imidazolium cations.

    PubMed

    Kofu, Maiko; Tyagi, Madhusudan; Inamura, Yasuhiro; Miyazaki, Kyoko; Yamamuro, Osamu

    2015-12-21

    Relaxation processes for imidazolium-based ionic liquids (ILs) were investigated by means of an incoherent quasielastic neutron scattering technique. In order to clarify the cation and anion effects on the relaxation processes, ten samples were measured. For all of the samples, we found three relaxations at around 1 ps, 10 ps, and 100 ps-10 ns, each corresponding to the alkyl reorientation, the relaxation related to the imidazolium ring, and the ionic diffusion. The activation energy (Ea) for the alkyl relaxation is insensitive to both anion and alkyl chain lengths. On the other hand, for the imidazolium relaxation and the ionic diffusion processes, Ea increases as the anion size decreases but is almost independent of the alkyl chain length. This indicates that the ionic diffusion and imidazolium relaxation are governed by the Coulombic interaction between the core parts of the cations (imidazolium ring) and the anions. This is consistent with the fact that the imidazolium-based ILs have nanometer scale structures consisting of ionic and neutral (alkyl chain) domains. It is also found that there is a clear correlation between the ionic diffusion and viscosity, indicating that the ionic diffusion is mainly associated with the glass transition which is one of the characteristics of imidazolium-based ILs. PMID:26696061

  3. Electronic spectra of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation and radical

    DOE PAGES

    Peter R. Craig; Miller, John R.; Havlas, Zdenek; Trujillo, Marianela; Rempala, Pawel; Kirby, James P.; Noll, Bruce C.; Michl, Josef

    2016-05-02

    In this study, properties of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation 1 and its tetra-o-fluoro derivative 1a have been measured and calculated. The B3LYP/TZP optimized geometry of the free cation 1 agrees with a single-crystal X-ray diffraction structure except that in the crystal one of the phenyl substituents is strongly twisted to permit a close-packing interaction of two of its hydrogens with a nearby BF–4 anion. The low-energy parts of the solution electronic absorption and magnetic circular dichroism (MCD) spectra of 1 and 1a have been interpreted by comparison with TD-DFT (B3LYP/TZP) results. Reduction or pulse radiolysis lead to a neutral 19-electron radical,more » whose visible absorption and MCD spectra have been recorded and interpreted as well. The reduction is facilitated by ~0.1 V upon going from 1 to 1a« less

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

    PubMed

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

    2015-01-01

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

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

    PubMed

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

    2016-05-28

    Our observation reveals the effects of divalent and trivalent cations on the higher-order structure of giant DNA (T4 DNA 166 kbp) by fluorescence microscopy. It was found that divalent cations, Mg(2+) and Ca(2+), inhibit DNA compaction induced by a trivalent cation, spermidine (SPD(3+)). On the other hand, in the absence of SPD(3+), divalent cations cause the shrinkage of DNA. As the control experiment, we have confirmed the minimum effect of monovalent cation, Na(+) on the DNA higher-order structure. We interpret the competition between 2+ and 3+ cations in terms of the change in the translational entropy of the counterions. For the compaction with SPD(3+), we consider the increase in translational entropy due to the ion-exchange of the intrinsic monovalent cations condensing on a highly charged polyelectrolyte, double-stranded DNA, by the 3+ cations. In contrast, the presence of 2+ cation decreases the gain of entropy contribution by the ion-exchange between monovalent and 3+ ions. PMID:27250329

  6. 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.

  7. Kinetics for Tautomerizations and Dissociations of Triglycine Radical Cations

    SciTech Connect

    Siu, Chi-Kit; Zhao, Junfang; Laskin, Julia; Chu, Ivan K.; Hopkinson, Alan C.; Siu , K W Michael

    2009-06-01

    Fragmentations of tautomers of the α-centered radical triglycine radical cation, [GGG*]+, [GG*G]+, and [G*GG]+, are charge-driven, giving b-type ions; these are processes that are facilitated by a mobile proton, as in the fragmentation of protonated triglycine (Rodriquez, C.F. et al. J. Am. Chem. Soc. 2001, 123, 3006 - 3012). By contrast, radical centers are less mobile. Two mechanisms have been examined theoretically utilizing density functional theory and Rice-Ramsperger-Kassel-Marcus modeling: (1) a direct hydrogen-atom migration between two α-carbons, and (2) a two-step proton migration involving a canonical [GGG]*+ as an intermediate. Predictions employing the latter mechanism are in good agreement with results of recent CID experiments (Chu, I.K. et al. J. Am. Chem. Soc. 2008, 130, 7862 - 7872).

  8. Mechanism of DNA release from cationic liposome/DNA complexes used in cell transfection.

    PubMed

    Xu, Y; Szoka, F C

    1996-05-01

    To understand how DNA is released from cationic liposome/DNA complexes in cells, we investigated which biomolecules mediate release of DNA from a complex with cationic liposomes. Release from monovalent[1,2-dioleoyl-3(1)-1(trimethylammonio)propane] or multivalent (dioctadecylamidoglycylspermine) lipids was quantified by an increase of ethidium bromide (EtBr) fluorescence. Plasmid sensitivity to DNAse I degradation was examined using changes in plasmid migration on agarose gel electrophoresis. Physical separation of the DNA from the cationic lipid was confirmed and quantified on sucrose density gradients. Anionic liposomes containing compositions that mimic the cytoplasmic-facing monolayer of the plasma membrane (e.g. phosphatidylserine) rapidly released DNA from the complex. Release occurred near a 1/1 charge ratio (-/+) and was unaffected by ionic strength or ion type. Water soluble molecules with a high negative linear charge density such as dextran sulfate or heparin also released DNA. However, ionic water soluble molecules such as ATP, tRNA, DNA, poly(glutamic acid), spermidine, spermine, or histone did not, even at 100-fold charge excess (-/+). On the basis of these results, we propose that after the cationic lipid/DNA complex is internalized into cells by endocytosis it destabilizes the endosomal membrane. Destabilization induces flip-flop of anionic lipids from the cytoplasmic-facing monolayer, which laterally diffuse into the complex and form a charge neutral ion pair with the cationic lipids. This results in displacement of the DNA from the cationic lipid and release of the DNA into cytoplasm. This mechanism accounts for a variety of observations on cationic lipid/DNA complex-cell interactions.

  9. The Essential Elements of Facilitation.

    ERIC Educational Resources Information Center

    Priest, Simon; Gass, Michael; Gillis, Lee

    Most organizations find it difficult to implement change, and only about 10 percent of learning from training and development experiences is actually applied in the workplace. This book advocates facilitation as a means of enhancing change and increasing productivity. Facilitation engages employees by enhancing the processes associated with their…

  10. Facilitating Dialogues about Racial Realities

    ERIC Educational Resources Information Center

    Quaye, Stephen John

    2014-01-01

    Background/Context: Facilitating dialogues about racial issues in higher education classroom settings continues to be a vexing problem facing postsecondary educators. In order for students to discuss race with their peers, they need skilled facilitators who are knowledgeable about racial issues and able to support students in these difficult…

  11. Cationic-modified cyclodextrin nanosphere/anionic polymer as flocculation/sorption systems.

    PubMed

    Xiao, Huining; Cezar, Norlito

    2005-03-15

    Simultaneous removal of dissolved and colloidal substances has been a challenging task. The cationic-modified beta-cyclodextrin nanospheres synthesized in this work, in conjunction with a water-soluble polyacrylamide-based anionic polymer, potentially provide a novel approach to address the problem. The cyclodextrin was rendered cationic using (2,3-epoxypropyl)trimethylammonium chloride as a reagent. The cationicity of the modified cyclodextrin and the reaction between cyclodextrin and the reagent were characterized by electrophoresis measurement, polyelectrolyte titration, and NMR. As a dual-component flocculation system, the cationic cyclodextrin/anionic polymer significantly induced clay flocculation, lowering the relative turbidity of the clay suspension over a wide pH range. Meanwhile, as a nanospherical absorbent, the modified cyclodextrins exhibited strong affinity toward aromatic compounds via inclusion complex formation in the hydrophobic cavities, which was monitored by UV spectroscopy. These systems facilitated the simultaneous removal of dissolved and colloidal substances, which was unachievable previously. In addition, the interaction between anionic polymers and the clay particles pretreated with cationic cyclodextrin was investigated in order to reveal the flocculation mechanism.

  12. Cationic-modified cyclodextrin nanosphere/anionic polymer as flocculation/sorption systems.

    PubMed

    Xiao, Huining; Cezar, Norlito

    2005-03-15

    Simultaneous removal of dissolved and colloidal substances has been a challenging task. The cationic-modified beta-cyclodextrin nanospheres synthesized in this work, in conjunction with a water-soluble polyacrylamide-based anionic polymer, potentially provide a novel approach to address the problem. The cyclodextrin was rendered cationic using (2,3-epoxypropyl)trimethylammonium chloride as a reagent. The cationicity of the modified cyclodextrin and the reaction between cyclodextrin and the reagent were characterized by electrophoresis measurement, polyelectrolyte titration, and NMR. As a dual-component flocculation system, the cationic cyclodextrin/anionic polymer significantly induced clay flocculation, lowering the relative turbidity of the clay suspension over a wide pH range. Meanwhile, as a nanospherical absorbent, the modified cyclodextrins exhibited strong affinity toward aromatic compounds via inclusion complex formation in the hydrophobic cavities, which was monitored by UV spectroscopy. These systems facilitated the simultaneous removal of dissolved and colloidal substances, which was unachievable previously. In addition, the interaction between anionic polymers and the clay particles pretreated with cationic cyclodextrin was investigated in order to reveal the flocculation mechanism. PMID:15721912

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

    PubMed

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

    2016-06-01

    Cu2-xTe nanocubes were used as starting seeds to access metal telluride nanocrystals by cation exchanges at room temperature. The coordination number of the entering cations was found to play an important role in dictating the reaction pathways. The exchanges with tetrahedrally coordinated cations (i.e., with coordination number 4), such as Cd(2+) or Hg(2+), yielded monocrystalline CdTe or HgTe nanocrystals with Cu2-xTe/CdTe or Cu2-xTe/HgTe Janus-like heterostructures as intermediates. The formation of Janus-like architectures was attributed to the high diffusion rate of the relatively small tetrahedrally coordinated cations, which could rapidly diffuse in the Cu2-xTe NCs and nucleate the CdTe (or HgTe) phase in a preferred region of the host structure. Also, with both Cd(2+) and Hg(2+) ions the exchange led to wurtzite CdTe and HgTe phases rather than the more stable zinc-blende ones, indicating that the anion framework of the starting Cu2-xTe particles could be more easily deformed to match the anion framework of the metastable wurtzite structures. As hexagonal HgTe had never been reported to date, this represents another case of metastable new phases that can only be accessed by cation exchange. On the other hand, the exchanges involving octahedrally coordinated ions (i.e., with coordination number 6), such as Pb(2+) or Sn(2+), yielded rock-salt polycrystalline PbTe or SnTe nanocrystals with Cu2-xTe@PbTe or Cu2-xTe@SnTe core@shell architectures at the early stages of the exchange process. In this case, the octahedrally coordinated ions are probably too large to diffuse easily through the Cu2-xTe structure: their limited diffusion rate restricts their initial reaction to the surface of the nanocrystals, where cation exchange is initiated unselectively, leading to core@shell architectures. Interestingly, these heterostructures were found to be metastable as they evolved to stable Janus-like architectures if annealed at 200 °C under vacuum. PMID:27177274

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

    PubMed

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

    2016-06-01

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

  15. Molecular dynamics simulation of diffusion and electrical conductivity in montmorillonite interlayers

    DOE PAGES

    Greathouse, Jeffery A.; Cygan, Randall T.; Fredrich, Joanne T.; Jerauld, Gary R.

    2016-01-20

    In this study, the diffusion of water and ions in the interlayer region of smectite clay minerals represents a direct probe of the type and strength of clay–fluid interactions. Interlayer diffusion also represents an important link between molecular simulation and macroscopic experiments. Here we use molecular dynamics simulation to investigate trends in cation and water diffusion in montmorillonite interlayers, looking specifically at the effects of layer charge, interlayer cation and cation charge (sodium or calcium), water content, and temperature. For Na-montmorillonite, the largest increase in ion and water diffusion coefficients occurs between the one-layer and two-layer hydrates, corresponding to themore » transition from inner-sphere to outer-sphere surface complexes. Calculated activation energies for ion and water diffusion in Na-montmorillonite are similar to each other and to the water hydrogen bond energy, suggesting the breaking of water–water and water–clay hydrogen bonds as a likely mechanism for interlayer diffusion. A comparison of interlayer diffusion with that of bulk electrolyte solutions reveals a clear trend of decreasing diffusion coefficient with increasing electrolyte concentration, and in most cases the interlayer diffusion results are nearly coincident with the corresponding bulk solutions. Trends in electrical conductivities computed from the ion diffusion coefficients are also compared.« less

  16. 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

  17. 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.

  18. Forging Colloidal Nanostructures via Cation Exchange Reactions

    PubMed Central

    2016-01-01

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

  19. Electromers of the benzene dimer radical cation.

    PubMed

    Błoch-Mechkour, Anna; Bally, Thomas

    2015-04-28

    The well-studied benzene dimer radical cation, which is prototypical for this class of species, has been reinvestigated computationally. Thereby it turned out that both the σ-hemibonded and the half-shifted sandwich structures of the benzene dimer cation, which had been independently proposed, represent stationary points on the B2PLYP-D potential energy surfaces. However, these structures belong to distinct electronic states, both of which are associated with potential surfaces that are very flat with regard to rotation of the two benzene rings in an opposite sense relative to each other. The surfaces of these two "electromers" of the benzene dimer cation are separated by only 3-4 kcal mol(-1) and do not intersect along the rotation coordinate, which represents a rather unique electronic structure situation. When moving on either of the two surfaces the title complex is an extremely fluxional species, in spite of its being bound by over 20 kcal mol(-1).

  20. 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

  1. NIST Diffusion Data Center

    National Institute of Standards and Technology Data Gateway

    NIST Diffusion Data Center (Web, free access)   The NIST Diffusion Data Center is a collection of over 14,100 international papers, theses, and government reports on diffusion published before 1980.

  2. Parallel flow diffusion battery

    DOEpatents

    Yeh, H.C.; Cheng, Y.S.

    1984-01-01

    A parallel flow diffusion battery for determining the mass distribution of an aerosol has a plurality of diffusion cells mounted in parallel to an aerosol stream, each diffusion cell including a stack of mesh wire screens of different density.

  3. Parallel flow diffusion battery

    DOEpatents

    Yeh, Hsu-Chi; Cheng, Yung-Sung

    1984-08-07

    A parallel flow diffusion battery for determining the mass distribution of an aerosol has a plurality of diffusion cells mounted in parallel to an aerosol stream, each diffusion cell including a stack of mesh wire screens of different density.

  4. Application of the pH-Imaging Sensor to Determining the Diffusion Coefficients of Ions in Electrolytic Solutions

    NASA Astrophysics Data System (ADS)

    Yoshinobu, Tatsuo; Harada, Tetsuro; Iwasaki, Hiroshi

    2000-04-01

    The pH-imaging sensor is applied to visualization of ionic diffusion in an electrochemical system. Redistribution of the pH value due to diffusion of ions after electrolysis is measured to determine the diffusion coefficients of anions and cations. Dependence of the diffusion coefficient on the molecular weight of ions is investigated. Applicability of the pH-imaging sensor to quantitative analysis of dynamics in a chemical system is demonstrated.

  5. 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.

  6. 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.

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

    NASA Astrophysics Data System (ADS)

    Lee, Min-Hong

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

  8. Sequestration of organic cations by acidified hepatic endocytic vesicles and implications for biliary excretion.

    PubMed

    Van Dyke, R W; Faber, E D; Meijer, D K

    1992-04-01

    A number of cationic amine drugs that are taken up by liver and excreted into bile may accumulate in acidified intracellular organelles such as lysosomes and endosomes. These studies were undertaken to assess directly the uptake and accumulation of three types of model organic cationic amines by endocytic vesicles, and the role of vesicle acidification in this process. Uptake of tubocurarine (TC), vecuronium and tributylmethylammonium (TBuMA) by purified rat liver multivesicular bodies (MVB) (prelysosomal endocytic vesicles) was dependent upon MgATP, time and drug concentration. After 60 min, 52 to 81% of MVB cation content was dependent upon vesicle acidification (due to an electrogenic proton pump), but not upon an interior positive vesicle membrane potential. Nineteen to 42% of MVB cation content appeared due to binding to MVB membranes or to internal lipoproteins. Vesicle-to-medium ATP-dependent apparent concentration ratios for these three cations were 3.3 to 51. MVB uptake of these cations resembled uptake of methylamine, a tertiary amine known to distribute across organellar membranes according to pH gradients. By contrast, MVB uptake of the lipophilic quaternary amine methyldeptropine was not dependent upon MgATP or on development of MVB pH or membrane potential gradients. In further studies, TC, vecuronium and TBuMA were rapidly taken up by the isolated perfused rat liver and excreted in bile. Exposure to 250 mciroM primaquin (which partially alkalinized acidic endosomes and lysosomes) reduced accumulation of [3H]vecuronium in a lysosomal fraction by 23%, decreased perfusate disappearance of TC and TBuMA, but not of vecuronium, and decreased biliary appearance of all three cations. These studies suggest that acidified intracellular organelles sequester certain organic cationic drugs, possibly via a drug/proton antiporter, and/or diffusion followed by intravesicular protonation and trapping of tertiary amines. However, attempts at partial displacement of

  9. Diffusing Diffusivity: A Model for Anomalous, yet Brownian, Diffusion

    NASA Astrophysics Data System (ADS)

    Chubynsky, Mykyta V.; Slater, Gary W.

    2014-08-01

    Wang et al. [Proc. Natl. Acad. Sci. U.S.A. 106, 15160 (2009)] have found that in several systems the linear time dependence of the mean-square displacement (MSD) of diffusing colloidal particles, typical of normal diffusion, is accompanied by a non-Gaussian displacement distribution G(x ,t), with roughly exponential tails at short times, a situation they termed "anomalous yet Brownian" diffusion. The diversity of systems in which this is observed calls for a generic model. We present such a model where there is diffusivity memory but no direction memory in the particle trajectory, and we show that it leads to both a linear MSD and a non-Gaussian G(x ,t) at short times. In our model, the diffusivity is undergoing a (perhaps biased) random walk, hence the expression "diffusing diffusivity". G(x ,t) is predicted to be exactly exponential at short times if the distribution of diffusivities is itself exponential, but an exponential remains a good fit for a variety of diffusivity distributions. Moreover, our generic model can be modified to produce subdiffusion.

  10. The cation-chelation mechanism of metal-ion sorption by polyurethanes.

    PubMed

    Hamon, R F; Khan, A S; Chow, A

    1982-04-01

    The mechanism of sorption of ions by polyurethanes has been investigated through detailed studies of the extraction of cobalt(II) thiocyanate and the salts of several organic acids. Polyether-based polyurethanes. particularly those containing poly(ethylene oxide), were found to be distinctly superior to polyesters in the sorption of salts and performed much better than might be expected by analogy with monomeric liquid solvents. The results were judged to be inconsistent with several possible mechanisms, including adsorption, solvent extraction, weak or strong base anion-exchange, and complexation of metal anions by the polymer. A new proposal, termed the cation chelation mechanism (CCM), was advanced to account for the observations. In this view, a number of cations (including those of the alkali metals, alkaline earth metals, some transition metals, NH(+)(4), RNH(+)(3) and perhaps H(3)O(+)) may be multiply complexed (chelated) by portions of the polymer, thus facilitating the sorption of accompanying anions. As predicted by the mechanism, moderately strong and selective complexation of several cations was observed to occur with the following order of selectivity: Li(+) < Na(+) < Cs(+) < Rb(+) < K(+) approximately NH(+)(4) < Ag(+) approximately Tl(+) < Ba(2+) < Hg(2+) < Pb(2+). Such behaviour parallels that known for many crown and non-cyclic polyethers and is therefore identified with the polyether portions of the polymer, which are thought to adopt helical conformations surrounding the complexed cations. The cation-chelation mechanism may be widely applicable to the sorption of ions of several types by polyether-based polyurethanes, particularly when large, hydrophobic anions (such as anionic metal complexes) are accompanied by an excess of chelatable cations. PMID:18963133

  11. 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

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

    PubMed

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

    2013-01-01

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

  13. 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.

  14. 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

  15. 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.

  16. 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.

  17. Anionic/cationic complexes in hair care.

    PubMed

    O'Lenick, Tony

    2011-01-01

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

  18. 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,...

  19. Evidence-based practice: how nurse leaders can facilitate innovation.

    PubMed

    Shirey, Maria R

    2006-01-01

    Evidence-based nursing practice (EBNP) is the wave of the future. Increasingly, EBNP is being identified as a key to quality and excellence in nursing services. Incorporating evidence into practice is necessary to deliver scientifically sound patient care. In addition, understanding the importance of evidence is crucial for meeting the excellence requirements of Magnet designation. Despite the growing popularity of EBNP and its documented significant benefits, the literature demonstrates that only 15% of the nursing workforce consistently practices within an EBNP framework. If EBNP adoption is to increase in the profession, it will require the active efforts of nurse leaders to pursue an aggressive innovation diffusion strategy. The purpose of this article is to discuss the nurse leader's role in facilitating EBNP in nursing using a theoretical framework grounded in innovation diffusion theory. The article develops 4 areas of focus. First, the components of innovation diffusion theory are discussed. Second, a pertinent empirical review of the EBNP adoption literature is presented. Third, strategies for applying innovation diffusion theory to facilitate EBNP adoption are proposed. Lastly, the article ends with a leadership call to action.

  20. 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.

  1. 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.

  2. Cationic lipids and cationic ligands induce DNA helix denaturation: detection of single stranded regions by KMnO4 probing.

    PubMed

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

    2003-09-25

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

  3. 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

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

    PubMed Central

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

    2015-01-01

    Soil particle interactions are strongly influenced by the concentration, valence and ion species and the pH of the bulk solution, which will also affect aggregate stability and particle transport. In this study, we investigated clay aggregate stability in the presence of different alkali ions (Li+, Na+, K+, and Cs+) at concentrations from10−5 to 10−1 mol L−1. Strong specific ion effects on clay aggregate stability were observed, and showed the order Cs+>K+>Na+>Li+. We found that it was not the effects of ion size, hydration, and dispersion forces in the cation–surface interactions but strong non-classic polarization of adsorbed cations that resulted in these specific effects. In this study, the non-classic dipole moments of each cation species resulting from the non-classic polarization were estimated. By comparing non-classic dipole moments with classic values, the observed dipole moments of adsorbed cations were up to 104 times larger than the classic values for the same cation. The observed non-classic dipole moments sharply increased with decreasing electrolyte concentration. We conclude that strong non-classic polarization could significantly suppress the thickness of the diffuse layer, thereby weakening the electric field near the clay surface and resulting in improved clay aggregate stability. Even though we only demonstrated specific ion effects on aggregate stability with several alkali ions, our results indicate that these effects could be universally important in soil aggregate stability. PMID:25874864

  5. Interfacial charge transfer mechanisms and cation effects in dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Staniszewski, Aaron J.

    The contents herein this thesis report on mechanistic processes important for the dye-sensitized solar cell (DSSC) with a focus on the influential nature of small cations at the interface. Chapter 1 introduces the reader to the DSSC by describing the accepted mechanism of a functioning cell and detailing its working components. Chapter 2 reports on a novel strategy aimed to improve device efficiencies and exceed the Shockley-Queisser limit, a well-known theoretical solar-to-electrical energy conversion efficiency standard. This strategy uses the ultrafast electron injection properties of the TiO2 to produce products from sunlight that are uphill in fluid solution. In Chapter 3, the mechanism of recombination of this charge-separated state is studied using chronoabsorption measurements. It is proposed that while the hole transport is limited through self-exchange reactions, the conduction band states of TiO2 mediate electron transport. Potential determining cations were introduced to "tune" the electron diffusion rates. Chapter 4 reports on a high-extinction ruthenium compound for its use as a sensitizer. Interestingly, after photo-oxidation of this compound on TiO2, the hole transferred out to a remote ligand, increasing the charge separation distance. Cation motion was studied in Chapter 5 using a novel ruthenium(II) compound that underwent large spectroscopic changes when exposed to lithium cations. These absorption changes allowed the determination of its transport mechanism at the interface during electron injection and charge recombination.

  6. Multi-physical model of cation and water transport in ionic polymer-metal composite sensors

    NASA Astrophysics Data System (ADS)

    Zhu, Zicai; Chang, Longfei; Horiuchi, Tetsuya; Takagi, Kentaro; Aabloo, Alvo; Asaka, Kinji

    2016-03-01

    Ion-migration based electrical potential widely exists not only in natural systems but also in ionic polymer materials. We presented a multi-physical model and investigated the transport process of cation and water of ionic polymer-metal composites based on our thorough understanding on the ionic sensing mechanisms in this paper. The whole transport process was depicted by transport equations concerning convection flux under the total pressure gradient, electrical migration by the built-in electrical field, and the inter-coupling effect between cation and water. With numerical analysis, the influence of critical material parameters, the elastic modulus Ewet, the hydraulic permeability coefficient K, the diffusion coefficient of cation dII and water dWW, and the drag coefficient of water ndW, on the distribution of cation and water was investigated. It was obtained how these parameters correlate to the voltage characteristics (both magnitude and response speed) under a step bending. Additionally, it was found that the effective relative dielectric constant ɛr has little influence on the voltage but is positively correlated to the current. With a series of optimized parameters, the predicted voltage agreed with the experimental results well, which validated our model. Based on our physical model, it was suggested that an ionic polymer sensor can benefit from a higher modulus Ewet, a higher coefficient K and a lower coefficient dII, and a higher constant ɛr.

  7. Effect of Sulfuric and Triflic Acids on the Hydration of Vanadium Cations: An ab Initio Study.

    PubMed

    Sepehr, Fatemeh; Paddison, Stephen J

    2015-06-01

    Vanadium redox flow batteries (VRFBs) may be a promising solution for large-scale energy storage applications, but the crossover of any of the redox active species V(2+), V(3+), VO(2+), and VO2(+) through the ion exchange membrane will result in self-discharge of the battery. Hence, a molecular level understanding of the states of vanadium cations in the highly acidic environment of a VRFB is needed. We examine the effects of sulfuric and triflic (CF3SO3H) acids on the hydration of vanadium species as they mimic the electrolyte and functional group of perfluorosulfonic acid (PFSA) membranes. Hybrid density functional theory in conjunction with a continuum solvation model was utilized to obtain the local structures of the hydrated vanadium cations in proximity to H2SO4, CF3SO3H, and their conjugate anions. The results indicate that none of these species covalently bond to the vanadium cations. The hydration structure of V(3+) is more distorted than that of V(2+) in an acidic medium. The oxo-group of VO2(+) is protonated by either acid, in contrast to VO(2+) which is not protonated. The atomic partial charge of the four oxidation states of vanadium varies from +1.7 to +2.0. These results provide the local solvation structures of vanadium cations in the VRFBs environment that are directly related to the electrolytes stability and diffusion of vanadium ions into the membrane. PMID:25954916

  8. Effect of Sulfuric and Triflic Acids on the Hydration of Vanadium Cations: An ab Initio Study.

    PubMed

    Sepehr, Fatemeh; Paddison, Stephen J

    2015-06-01

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

  9. Comparison of the hammerhead cleavage reactions stimulated by monovalent and divalent cations.

    PubMed Central

    O'Rear, J L; Wang, S; Feig, A L; Beigelman, L; Uhlenbeck, O C; Herschlag, D

    2001-01-01

    Although the hammerhead reaction proceeds most efficiently in divalent cations, cleavage in 4 M LiCl is only approximately 10-fold slower than under standard conditions of 10 mM MgCl2 (Murray et al., Chem Biol, 1998, 5:587-595; Curtis & Bartel, RNA, 2001, this issue, pp. 546-552). To determine if the catalytic mechanism with high concentrations of monovalent cations is similar to that with divalent cations, we compared the activities of a series of modified hammerhead ribozymes in the two ionic conditions. Nearly all of the modifications have similar deleterious effects under both reaction conditions, suggesting that the hammerhead adopts the same general catalytic structure with both monovalent and divalent cations. However, modification of three ligands previously implicated in the binding of a functional divalent metal ion have substantially smaller effects on the cleavage rate in Li+ than in Mg2+. This result suggests that an interaction analogous to the interaction made by this divalent metal ion is absent in the monovalent reaction. Although the contribution of this divalent metal ion to the overall reaction rate is relatively modest, its presence is needed to achieve the full catalytic rate. The role of this ion appears to be in facilitating formation of the active structure, and any direct chemical role of metal ions in hammerhead catalysis is small. PMID:11345432

  10. 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.

  11. 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.

  12. Sorption mechanism and predictive models for removal of cationic organic contaminants by cation exchange resins.

    PubMed

    Jadbabaei, Nastaran; Zhang, Huichun

    2014-12-16

    Understanding the sorption mechanism of organic contaminants on cation exchange resins (CXRs) will enable application of these resins for the removal of cationic organic compounds from contaminated water. In this study, sorption of a diverse set of 12 organic cations and 8 neutral aromatic solutes on two polystyrene CXRs, MN500 and Amberlite 200, was examined. MN500 showed higher sorbed concentrations due to its microporous structure. The sorbed concentrations followed the same trend of aromatic cations > aliphatic cations > neutral solutes for both resins. Generally, solute-solvent interactions, nonpolar moiety of the solutes, and resin matrix can affect selectivity of the cations. Sorbed concentrations of the neutral compounds were significantly less than those of the cations, indicating a combined effect of electrostatic and nonelectrostatic interactions. By conducting multiple linear regression between Gibbs free energy of sorption and Abraham descriptors for all 20 compounds, polarity/polarizability (S), H-bond acidity (A), induced dipole (E), and electrostatic (J(+)) interactions were found to be involved in the sorption of the cations by the resins. After converting the aqueous sorption isotherms to sorption from the ideal gas-phase by water-wet resins, a more significant effect of J(+) was observed. Predictive models were then developed based on the linear regressions and validated by accurately estimating the sorption of different test set compounds with a root-mean-square error range of 0.91-1.1 and 0.76-0.85 for MN500 and Amberlite 200, respectively. The models also accurately predicted sorption behavior of aniline and imidazole between pH 3 and 10. PMID:25409479

  13. Effects of cation on electrical responses of ionic polymer-metal composite sensors at various ambient humidities

    NASA Astrophysics Data System (ADS)

    Zhu, Zicai; Horiuchi, Tetsuya; Takagi, Kentaro; Takeda, Jun; Chang, Longfei; Asaka, Kinji

    2016-08-01

    In this study, we investigated the effects of various cations on the electrical responses of ionic polymer-metal composite (IPMC) sensors at various ambient humidities. Four typical Au-Nafion IPMC samples were prepared with H+, Li+, Na+, and K+ cations. The voltage and current responses of the IPMCs were investigated under static and dynamic bending displacements. The orders of the voltage and current amplitudes were generally Li+ > Na+ > K+ > H+ and depended on the cation transport properties and the water content. The static voltage response first increased to a peak and then slowly decreased to a steady state. A negative steady-state voltage was initially observed for the IPMC with H+ cations under near saturation conditions. The voltage amplitude increased monotonously with increasing frequency from 0.1 to 10 Hz at a high relative humidity (RH, ˜90%), first increased and then decreased at moderate humidity (RH, ˜50%), and decreased continuously at low humidity (RH, ˜20%). The static current response first rapidly increased to a peak and then quickly decayed. During current decay, free oscillation decay occurred at high humidity and attenuated with decreasing humidity. This was confirmed to be the result of cation movement in the IPMC. There are three necessary conditions for oscillation: sufficient migrated cations, high cation mobility, and high stiffness of the polymer network. For the dynamic current response, the amplitude increased with increasing frequency (0.1-10 Hz) and showed good linearity. The underlying physics, mainly involving cation forward migration and back diffusion caused by mechano-chemo-electrical coupling, was clarified.

  14. Rare earth element diffusion in apatite

    NASA Astrophysics Data System (ADS)

    Cherniak, D. J.

    2000-11-01

    ) may be attributable to the differences in substitutional processes facilitating REE exchange. The fastest diffusion, found in the ion-implantation experiments, is likely largely governed by simple light REE +3 ↔ REE +3 exchange, with no charge compensating species necessary. REE transport in the in-diffusion experiments requires movement of an additional charge-compensating species, either through the substitutions REE +3 + Si +4 ↔ Ca +2 + P +5 or REE +3 + Na +1 ↔ 2 Ca +2, and thus proceeds more slowly than simple REE exchange. Slowest of all is Nd out-diffusion from the synthetic Nd-doped apatite, for which neither charge compensating species are present nor REEs available in the surrounding reservoir to facilitate Nd exchange. This observed dependence of REE diffusion rates on the exchange process involved has important geochemical implications. These findings indicate that REE isotope and chemical signatures can become decoupled in apatite, with light REE isotope exchange proceeding much more rapidly than REE chemical diffusion altering total REE concentrations. Under temperatures typical of thermal events, REE zoning (involving differences in REE concentration across zones) of a given dimension might persist over time periods two orders of magnitude greater than those under which zoning of REE isotopes (without significant changes in total REE) on similar scale is preserved.

  15. High School Facilitators and Inhibitors.

    ERIC Educational Resources Information Center

    Gnagey, William J.

    1981-01-01

    Teachers in a small high school nominated students whose classroom behavior facilitates or inhibits (disrupts) the learning process. These two groups were compared on locus of control, Maslow motive hierarchies, attitudes toward crime prevention, and achievement. Results are discussed and suggestions for helping disruptive students are made. (SJL)

  16. Sign Facilitation in Word Recognition.

    ERIC Educational Resources Information Center

    Wauters, Loes N.; Knoors, Harry E. T.; Vervloed, Mathijs P. J.; Aarnoutse, Cor A. J.

    2001-01-01

    This study examined whether use of sign language would facilitate reading word recognition by 16 deaf children (6- to 1 years-old) in the Netherlands. Results indicated that if words were learned through speech, accompanied by the relevant sign, accuracy of word recognition was greater than if words were learned solely through speech. (Contains…

  17. Producing Gestures Facilitates Route Learning

    PubMed Central

    So, Wing Chee; Ching, Terence Han-Wei; Lim, Phoebe Elizabeth; Cheng, Xiaoqin; Ip, Kit Yee

    2014-01-01

    The present study investigates whether producing gestures would facilitate route learning in a navigation task and whether its facilitation effect is comparable to that of hand movements that leave physical visible traces. In two experiments, we focused on gestures produced without accompanying speech, i.e., co-thought gestures (e.g., an index finger traces the spatial sequence of a route in the air). Adult participants were asked to study routes shown in four diagrams, one at a time. Participants reproduced the routes (verbally in Experiment 1 and non-verbally in Experiment 2) without rehearsal or after rehearsal by mentally simulating the route, by drawing it, or by gesturing (either in the air or on paper). Participants who moved their hands (either in the form of gestures or drawing) recalled better than those who mentally simulated the routes and those who did not rehearse, suggesting that hand movements produced during rehearsal facilitate route learning. Interestingly, participants who gestured the routes in the air or on paper recalled better than those who drew them on paper in both experiments, suggesting that the facilitation effect of co-thought gesture holds for both verbal and nonverbal recall modalities. It is possibly because, co-thought gesture, as a kind of representational action, consolidates spatial sequence better than drawing and thus exerting more powerful influence on spatial representation. PMID:25426624

  18. Producing gestures facilitates route learning.

    PubMed

    So, Wing Chee; Ching, Terence Han-Wei; Lim, Phoebe Elizabeth; Cheng, Xiaoqin; Ip, Kit Yee

    2014-01-01

    The present study investigates whether producing gestures would facilitate route learning in a navigation task and whether its facilitation effect is comparable to that of hand movements that leave physical visible traces. In two experiments, we focused on gestures produced without accompanying speech, i.e., co-thought gestures (e.g., an index finger traces the spatial sequence of a route in the air). Adult participants were asked to study routes shown in four diagrams, one at a time. Participants reproduced the routes (verbally in Experiment 1 and non-verbally in Experiment 2) without rehearsal or after rehearsal by mentally simulating the route, by drawing it, or by gesturing (either in the air or on paper). Participants who moved their hands (either in the form of gestures or drawing) recalled better than those who mentally simulated the routes and those who did not rehearse, suggesting that hand movements produced during rehearsal facilitate route learning. Interestingly, participants who gestured the routes in the air or on paper recalled better than those who drew them on paper in both experiments, suggesting that the facilitation effect of co-thought gesture holds for both verbal and nonverbal recall modalities. It is possibly because, co-thought gesture, as a kind of representational action, consolidates spatial sequence better than drawing and thus exerting more powerful influence on spatial representation. PMID:25426624

  19. Facilitating Creativity in Adult Learners

    ERIC Educational Resources Information Center

    Tsai, Kuan Chen

    2013-01-01

    Creativity in education research has received increasing attention, although the major focus of this research has been on children. Despite pleas by several adult educators for promoting creativity, very few studies have focused on adult learners, leaving to it to be explored what approaches are useful for adult educators to facilitate creativity…

  20. SUPERFUND GROUNDWATER ISSUE - FACILITATED TRANSPORT

    EPA Science Inventory

    The Regional Superfund Ground Water Forum is a group of ground-water scientists representing EPA's Regional Superfund Offices, organized to exchange up to date information related to ground-water remediation at Superfund sites. Facilitated transport is an issue identified by the ...

  1. Facilitation of Mourning During Childhood.

    ERIC Educational Resources Information Center

    Kliman, Gilbert; And Others

    This paper discusses case studies of children psychologically disturbed by the death of parents or siblings. Illustrations of mourning facilitation were mainly gathered from 16 orphaned children, ages 3-14. Some techniques used in helping children mourn include: discussing physical details of the illness, discussing previous deaths of animals and…

  2. Social Facilitation of Aiding Responses.

    ERIC Educational Resources Information Center

    Bartell, Patricia; And Others

    Research on individual's response to emergency situations in the presence of others has produced conflicting results. The bystander effect is the label applied to inaction or the unlikelihood of assistance with others present. The social facilitation effect occurs when the presence of others energizes response; strong habit responses are…

  3. Improving the alkaline stability of imidazolium cations by substitution.

    PubMed

    Dong, Huilong; Gu, Fenglou; Li, Min; Lin, Bencai; Si, Zhihong; Hou, Tingjun; Yan, Feng; Lee, Shuit-Tong; Li, Youyong

    2014-10-01

    Imidazolium cations are promising candidates for preparing anion-exchange membranes because of their good alkaline stability. Substitution of imidazolium cations is an efficient way to improve their alkaline stability. By combining density functional theory calculations with experimental results, it is found that the LUMO energy correlates with the alkaline stability of imidazolium cations. The results indicate that alkyl groups are the most suitable substituents for the N3 position of imidazolium cations, and the LUMO energies of alkyl-substituted imidazolium cations depend on the electron-donating effect and the hyperconjugation effect. Comparing 1,2-dimethylimidazolium cations (1,2-DMIm+) and 1,3-dimethylimidazolium cations (1,3-DMIm+) with the same substituents reveals that the hyperconjugation effect is more significant in influencing the LUMO energy of 1,3-DMIms. This investigation reveals that LUMO energy is a helpful aid in predicting the alkaline stability of imidazolium cations.

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

    PubMed

    Cheng, Hong; Liang, Ran; Han, Rui-Min; Zhang, Jian-Ping; Skibsted, Leif H

    2014-02-01

    The radical cation generated during photobleaching of β-carotene is scavenged efficiently by the anion of methyl salicylate from wintergreen oil in a second-order reaction approaching the diffusion limit with k2 = 3.2 × 10(9) L mol(-1) s(-1) in 9 : 1 v/v chloroform-methanol at 23 °C, less efficiently by the anion of salicylic acid with 2.2 × 10(8) L mol(-1) s(-1), but still of possible importance for light-exposed tissue. Surprisingly, acetylsalicylate, the aspirin anion, reacts with an intermediate rate in a reaction assigned to the anion of the mixed acetic-salicylic acid anhydride formed through base induced rearrangements. The relative scavenging rate of the β-carotene radical cation by the three salicylates is supported by DFT-calculations.

  5. Molecular dynamics simulation of imidazolium-based ionic liquids. I. Dynamics and diffusion coefficient

    NASA Astrophysics Data System (ADS)

    Kowsari, M. H.; Alavi, Saman; Ashrafizaadeh, Mahmud; Najafi, Bijan

    2008-12-01

    Molecular dynamics simulations are used to study the dynamics and transport properties of 12 room-temperature ionic liquids of the 1-alkyl-3-methylimidazolium [amim]+ (alkyl=methyl, ethyl, propyl, and butyl) family with PF6-, NO3-, and Cl- counterions. The explicit atom transferable force field of Canongia Lopes et al. [J. Phys. Chem. B 108, 2038 (2004)] is used in the simulations. In this first part, the dynamics of the ionic liquids are characterized by studying the mean-square displacement (MSD) and the velocity autocorrelation function (VACF) for the centers of mass of the ions at 400 K. Trajectory averaging was employed to evaluate the diffusion coefficients at two temperatures from the linear slope of MSD(t) functions in the range of 150-300 ps and from the integration of the VACF(t) functions at 400 K. Detailed comparisons are made between the diffusion results from the MSD and VACF methods. The diffusion coefficients from the integration of the VACFs are closer to experimental values than the diffusion coefficients calculated from the slope of MSDs. Both methods can show good agreement with experiment in predicting relative trends in the diffusion coefficients and determining the role of the cation and anion structures on the dynamical behavior of this family of ionic liquids. The MSD and self-diffusion of relatively heavier imidazolium cations are larger than those of the lighter anions from the Einstein results, except for the case of [bmim][Cl]. The cationic transference number generally decreases with temperature, in good agreement with experiments. For the same anion, the cationic transference numbers decrease with increasing length of the alkyl chain, and for the same cation, the trends in the cationic transference numbers are [NO3]-<[Cl]-<[PF6]-. The trends in the diffusion coefficient in the series of cations with identical anions are [emim]+>[pmim]+>[bmim]+ and those for anions with identical cations are [NO3]->[PF6]->[Cl]-. The [dmim]+ has a

  6. Communication: CO oxidation by silver and gold cluster cations: Identification of different active oxygen species

    SciTech Connect

    Popolan, Denisia M.; Bernhardt, Thorsten M.

    2011-03-07

    The oxidation of carbon monoxide with nitrous oxide on mass-selected Au{sub 3}{sup +} and Ag{sub 3}{sup +} clusters has been investigated under multicollision conditions in an octopole ion trap experiment. The comparative study reveals that for both gold and silver cations carbon dioxide is formed on the clusters. However, whereas in the case of Au{sub 3}{sup +} the cluster itself acts as reactive species that facilitates the formation of CO{sub 2} from N{sub 2}O and CO, for silver the oxidized clusters Ag{sub 3}O{sub x}{sup +} (n= 1-3) are identified as active in the CO oxidation reaction. Thus, in the case of the silver cluster cations N{sub 2}O is dissociated and one oxygen atom is suggested to directly react with CO, whereas a second kind of oxygen strongly bound to silver is acting as a substrate for the reaction.

  7. 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.

  8. Facilitating Facilitators to Facilitate, in Problem or Enquiry Based Learning Sessions

    ERIC Educational Resources Information Center

    Coelho, Catherine

    2014-01-01

    Problem based learning (PBL) has been used in dental education over the past 20 years and uses a patient case scenario to stimulate learning in a small group setting, where a trained facilitator does not teach but guides the group to bring about deep contextualized learning, to be empathetic to each other and to encourage fair and equitable…

  9. Diffusive transport through compacted Na- and Ca-bentonite

    NASA Astrophysics Data System (ADS)

    Choi, J.-W.; Oscarson, D. W.

    1996-04-01

    The effect of exchangeable cation — Na + and Ca 2+ — on the diffusive transport of I -, Sr 2+ and 3H (as HTO) in compacted bentonite was examined using a through-diffusion method. Total intrinsic diffusion coefficients, Di, were determined from the steady-state flux of the diffusants through the clays, and apparent diffusion coefficients, Da, were obtained from the time lag technique. The clays were compacted to a dry bulk density of 1.3 Mg/m 3, and Na-bentonite was saturated with a solution of 100 mol NaCl/m3 and Ca-bentonite with one of 50 mol CaCl 2/m 3. The Di values for all diffusants are 2 to 6 times higher in the Ca- than Na-clay. We attribute this to the larger quasicrystal, or particle, size of Ca- compared to Na-bentonite. Hence, Ca-bentonite has a greater proportion of relatively large pores; this was confirmed by Hg intrusion porosimetry. This means the diffusion pathways in Ca-bentonite are less tortuous than those in Na-bentonite. Moreover, in some cases the effective porosity, or the porosity available for diffusive transport, may be greater in Ca-bentonite. The D a values are inversely proportional to the distribution coefficients of the diffusants with the clays.

  10. Diffusion model of the non-stoichiometric uranium dioxide

    SciTech Connect

    Moore, Emily; Guéneau, Christine; Crocombette, Jean-Paul

    2013-07-15

    Uranium dioxide (UO{sub 2}), which is used in light water reactors, exhibits a large range of non-stoichiometry over a wide temperature scale up to 2000 K. Understanding diffusion behavior of uranium oxides under such conditions is essential to ensure safe reactor operation. The current understanding of diffusion properties is largely limited by the stoichiometric deviations inherent to the fuel. The present DICTRA-based model considers diffusion across non-stoichiometric ranges described by experimentally available data. A vacancy and interstitial model of diffusion is applied to the U–O system as a function of its defect structure derived from CALPHAD-type thermodynamic descriptions. Oxygen and uranium self and tracer diffusion coefficients are assessed for the construction of a mobility database. Chemical diffusion coefficients of oxygen are derived with respect to the Darken relation and migration energies of defects are evaluated as a function of stoichiometric deviation. - Graphical abstract: Complete description of Oxygen–Uranium diffusion as a function of composition at various temperatures according to the developed Dictra model. - Highlights: • Assessment of a uranium–oxygen diffusion model with Dictra. • Complete description of U–O diffusion over wide temperature and composition range. • Oxygen model includes terms for interstitial and vacancy migration. • Interaction terms between defects help describe non-stoichiometric domain of UO{sub 2±x}. • Uranium model is separated into mobility terms for the cationic species.

  11. 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

  12. Low Cation Coordination in Oxide Melts

    NASA Astrophysics Data System (ADS)

    Skinner, L. B.; Benmore, C. J.; Weber, J. K. R.; Du, J.; Neuefeind, J.; Tumber, S. K.; Parise, J. B.

    2014-04-01

    The complete set of partial pair distribution functions for a rare earth oxide liquid are measured by combining aerodynamic levitation, neutron and x-ray diffraction on Y2O3, and Ho2O3 melts at 2870 K. The average Y-O (or Ho-O) coordination of these isomorphic melts is measured to be 5.5(2), which is significantly less than the octahedral coordination of crystalline Y2O3 (or Ho2O3). Investigation of La2O3, ZrO2, and Al2O3 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 coordination compared to their crystalline counterparts. It is found that the coordination drop is larger for lower field strength, larger radius cations and is negligible for high field strength (network forming) cations, such as SiO2. These findings have broad implications for predicting the local structure and related physical properties of metal-oxide melts and oxide glasses.

  13. Low cation coordination in oxide melts.

    PubMed

    Skinner, L B; Benmore, C J; Weber, J K R; Du, J; Neuefeind, J; Tumber, S K; Parise, J B

    2014-04-18

    The complete set of partial pair distribution functions for a rare earth oxide liquid are measured by combining aerodynamic levitation, neutron and x-ray diffraction on Y2O3, and Ho2O3 melts at 2870 K. The average Y-O (or Ho-O) coordination of these isomorphic melts is measured to be 5.5(2), which is significantly less than the octahedral coordination of crystalline Y2O3 (or Ho2O3). Investigation of La2O3, ZrO2, and Al2O3 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 coordination compared to their crystalline counterparts. It is found that the coordination drop is larger for lower field strength, larger radius cations and is negligible for high field strength (network forming) cations, such as SiO2. These findings have broad implications for predicting the local structure and related physical properties of metal-oxide melts and oxide glasses. PMID:24785072

  14. 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.

  15. Enhancement of deoxyribozyme activity by cationic copolymers.

    PubMed

    Gao, Jueyuan; Shimada, Naohiko; Maruyama, Atsushi

    2015-02-01

    Deoxyribozymes, or DNAzymes, are DNA molecules with enzymatic activity. DNAzymes with ribonuclease activity have various potential applications in biomedical and bioanalytical fields; however, most constructs have limited turnover despite optimization of reaction conditions and DNAzyme structures. A cationic comb-type copolymer accelerates DNA hybridization and strand exchange rates, and we hypothesized that the copolymer would enhance deoxyribozyme activity by promoting turnover. The copolymer did not change DNAzyme activity under single-turnover conditions, suggesting that the copolymer affects neither the folding structure of DNAzyme nor the association of a divalent cation, a catalytic cofactor, to DNAzyme. The copolymer enhanced activity of the evaluated DNAzyme over a wide temperature range under multiple-turnover conditions. The copolymer increased the DNAzyme kcat/KM by fifty-fold at 50 °C, the optimal temperature for the DNAzyme in the absence of the copolymer. The acceleration effect was most significant when the reaction temperature was slightly higher than the melting temperature of the enzyme/substrate complex; acceleration of two orders of magnitude was observed. We concluded that the copolymer accelerated the turnover step without influencing the chemical cleavage step. In contrast to the copolymer, a cationic surfactant, CTAB, strongly inhibited the DNAzyme activity under either single- or multiple-turnover conditions. PMID:26218121

  16. Microfabricated diffusion source

    DOEpatents

    Oborny, Michael C.; Frye-Mason, Gregory C.; Manginell, Ronald P.

    2008-07-15

    A microfabricated diffusion source to provide for a controlled diffusion rate of a vapor comprises a porous reservoir formed in a substrate that can be filled with a liquid, a headspace cavity for evaporation of the vapor therein, a diffusion channel to provide a controlled diffusion of the vapor, and an outlet to release the vapor into a gas stream. The microfabricated diffusion source can provide a calibration standard for a microanalytical system. The microanalytical system with an integral diffusion source can be fabricated with microelectromechanical systems technologies.

  17. How the spontaneous insertion of amphiphilic imidazolium-based cations changes biological membranes: a molecular simulation study.

    PubMed

    Lim, Geraldine S; Jaenicke, Stephan; Klähn, Marco

    2015-11-21

    The insertion of 1-octyl-3-methylimidazolium cations (OMIM(+)) from a diluted aqueous ionic liquid (IL) solution into a model of a bacterial cell membrane is investigated. Subsequently, the mutual interactions of cations inside the membrane and their combined effect on membrane properties are derived. The ionic liquid solution and the membrane model are simulated using molecular dynamics in combination with empirical force fields. A high propensity of OMIM(+) for membrane insertion is observed, with a cation concentration at equilibrium inside the membrane 47 times larger than in the solvent. Once inserted, cations exhibit a weak effective attraction inside the membrane at a distance of 1.3 nm. At this free energy minimum, negatively charged phosphates of the phospholipids are sandwiched between two OMIM(+) to form energetically favorable OMIM(+)-phosphate-OMIM(+) types of coordination. The cation-cation association free energy is 5.9 kJ mol(-1), whereas the activation barrier for dissociation is 10.1 kJ mol(-1). Subsequently, OMIM(+) are inserted into the leaflet of the membrane bilayer that represents the extracellular side. The cations are evenly distributed with mutual cation distances according to the found optimum distance of 1.3 nm. Because of the short length of the cation alkyl chains compared to lipid fatty acids, voids are generated in the hydrophobic core of the membrane. These voids disorder the fatty acids, because they enable fatty acids to curl into these empty spaces and also cause a thinning of the membrane by 0.6 nm. Additionally, the membrane density increases at its center. The presence of OMIM(+) in the membrane facilitates the permeation of small molecules such as ammonia through the membrane, which is chosen as a model case for small polar solutes. The permeability coefficient of the membrane with respect to ammonia increases substantially by a factor of seven. This increase is caused by a reduction of the involved free energy barriers

  18. Proton and cation transport activity of the M2 proton channel from influenza A virus.

    PubMed

    Leiding, Thom; Wang, Jun; Martinsson, Jonas; DeGrado, William F; Arsköld, Sindra Peterson

    2010-08-31

    The M2 protein is a small, single-span transmembrane (TM) protein from the influenza A virus. This virus enters cells via endosomes; as the endosomes mature and become more acidic M2 facilitates proton transport into the viral interior, thereby disrupting matrix protein/RNA interactions required for infectivity. A mystery has been how protons can accumulate in the viral interior without developing a large electrical potential that impedes further inward proton translocation. Progress in addressing this question has been limited by the availability of robust methods of unidirectional insertion of the protein into virus-like vesicles. Using an optimized procedure for reconstitution, we show that M2 has antiporter-like activity, facilitating K(+) or Na(+) efflux when protons flow down a concentration gradient into the vesicles. Cation efflux is very small except under conditions mimicking those encountered by the endosomally entrapped virus, in which protons are flowing through the channel. This proton/cation exchange function is consistent with the known high proton selectivity of the channel. Thus, M2 acts as a proton uniporter that occasionally allows K(+) to flow to maintain electrical neutrality. Remarkably, as the pH inside M2-containing vesicles (pH(in)) decreases, the proton channel activity of M2 is inhibited, but its cation transport activity is activated. This reciprocal inhibition of proton flux and activation of cation flux with decreasing pH(in) first allows accumulation of protons in the early stages of acidification, then trapping of protons within the virus when low pH(in) is achieved.

  19. Counterfactual Thinking Facilitates Behavioral Intentions

    PubMed Central

    Smallman, Rachel; Roese, Neal J.

    2009-01-01

    People often ponder what might have been, and these counterfactual inferences have been linked to behavior regulation. Counterfactuals may enhance performance by either a content-specific pathway (via shift in behavioral intentions) and/or a content-neutral pathway (via mindsets or motivation). Three experiments provided new specification of the content-specific pathway. A sequential priming paradigm revealed that counterfactual judgments facilitated RTs to complete behavioral intention judgments relative to control judgments and to a no-judgment baseline (Experiment 1). This facilitation effect was found only for intention judgments that matched the information content of the counterfactual (Experiment 2) and only for intention judgments as opposed to a different judgment that nevertheless focused on the same information content (Experiment 3). These findings clarify the content-specific pathway by which counterfactuals influence behavior. PMID:20161221

  20. Sign Crossover in All Maxwell-Stefan Diffusivities for Molten Salt LiF-BeF2: A Molecular Dynamics Study.

    PubMed

    Chakraborty, Brahmananda

    2015-08-20

    Applying Green-Kubo formalism and equilibrium molecular dynamics (MD) simulations, we have studied for the first time the dynamic correlation, Onsager coefficients, and Maxwell-Stefan (MS) diffusivities of molten salt LiF-BeF2, which is a potential candidate for a coolant in a high temperature reactor. We observe an unusual composition dependence and strikingly a crossover in sign for all the MS diffusivities at a composition of around 7% of LiF where the MS diffusivity between cation-anion pair (Đ(BeF) and Đ(LiF)) jumps from positive to negative value while the MS diffusivity between cation-cation pair (Đ(LiBe)) becomes positive from a negative value. Even though the negative MS diffusivities have been observed for electrolyte solutions between cation-cation pair, here we report negative MS diffusivity between cation-anion pair where Đ(BeF) shows a sharp rise around 66% of BeF2, reaches maximum value at 70% of BeF2, and then decreases almost exponentially with a sign change for BeF2 around 93%. For low mole fraction of LiF, Đ(BeF) follows the Debye-Huckel theory and rises with the square root of LiF mole fraction similar to the MS diffusivity between cation-anion pair in aqueous solution of electrolyte salt. Negative MS diffusivities while unusual are, however, shown to satisfy the non-negative entropy constraints at all thermodynamic states as required by the second law of thermodynamics. We have established a strong correlation between the structure and dynamics and predict that the formation of flouride polyanion network between Be and F ions and coulomb interaction is responsible for sharp variation of the MS diffusivities which controls the multicomponent diffusion phenomenon in LiF-BeF2 which has a strong impact on the performance of the reactor.

  1. Cation size effects in mixed-ion metaphosphate glasses: structural characterization by multinuclear solid state NMR spectroscopy.

    PubMed

    Schneider, J; Tsuchida, J; Eckert, H

    2013-09-14

    slowing down of the Ag(+) diffusion dynamics as this species is replaced by Cs(+) or Na(+). The substitution by the bigger Cs(+) ion causes a strong reduction in Ag(+) mobility suggesting the existence of separated diffusion pathways for these cations. In contrast, substitution by the similarly-sized Na(+) causes a much weaker mobility reduction consistent with the existence of Ag-Na cooperative hopping.

  2. Alkali cation specific adsorption onto fcc(111) transition metal electrodes.

    PubMed

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

    2014-07-21

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

  3. Gas-phase electronic spectrum of the indole radical cation

    NASA Astrophysics Data System (ADS)

    Chalyavi, N.; Catani, K. J.; Sanelli, J. A.; Dryza, V.; Bieske, E. J.

    2015-08-01

    The visible and near-UV electronic spectrum of the indole radical cation is measured in the gas phase by photodissociation of indole+-Ar and indole+-He complexes in a tandem mass spectrometer. A series of resolved vibronic transitions extending from 610 to 460 nm are assigned to the D2 ← D0 band system, while weak transitions between 390 and 360 nm are assigned to the D3 ← D0 system, and a stronger, broad, unresolved absorption between 350 and 300 nm is attributed to the D4 ← D0 system. Time-dependent density functional theory calculations are used to assign vibronic structure of the D2 ← D0 band system, and show that the main active vibrational modes correspond to in-plane ring deformations. The strongest D2 ← D0 vibronic transitions of indole+-He do not correspond with any catalogued diffuse interstellar bands, even considering band displacements of up to 50 cm-1possibly caused by the attached He atom.

  4. Antimicrobial activity of cationic peptides in endodontic procedures

    PubMed Central

    Winfred, Sofi Beaula; Meiyazagan, Gowri; Panda, Jiban J.; Nagendrababu, Venkateshbabu; Deivanayagam, Kandaswamy; Chauhan, Virander S.; Venkatraman, Ganesh

    2014-01-01

    Objectives: The present study aimed to investigate the antimicrobial and biofilm inhibition activity of synthetic antimicrobial peptides (AMPs) against microbes such as Enterococcus faecalis, Staphylococcus aureus, and Candida albicans which are involved in endodontic infections. Materials and Methods: Agar diffusion test was done to determine the activity of peptides. The morphological changes in E. faecalis and reduction in biofilm formation after treatment with peptides were observed using scanning electron microscope. The efficacy of peptides using an ex vivo dentinal model was determined by polymerase chain reaction and confocal laser scanning microscopy. Platelet aggregation was done to determine the biocompatibility of peptides. Results: Among 11 peptides, two of the amphipathic cationic peptides were found to be highly active against E. faecalis, S. aureus, C. albicans. Efficacy results using dentinal tubule model showed significant reduction in microbial load at 400 μm depth. The peptides were also biocompatible. Conclusion: These results suggest that synthetic AMPs have the potential to be developed as antibacterial agents against microorganisms involved in dental infections and thus could prevent the spread and persistence of endodontic infections improving treatment outcomes and teeth preservation. PMID:24966779

  5. Effects of two cations on gastrointestinal absorption of ofloxacin.

    PubMed Central

    Martínez Cabarga, M; Sánchez Navarro, A; Colino Gandarillas, C I; Domínguez-Gil, A

    1991-01-01

    A study was performed to establish the effect of Al3+ and Fe2+ cations on the absorption of ofloxacin when it is administered orally at a dose of 200 mg. The study was carried out with nine volunteers, who each received three treatments (A [200 mg of ofloxacin], B [200 mg of ofloxacin plus 11 g of colloidal aluminum phosphate], and C [200 mg of ofloxacin plus 1,050 mg of FeSO4]) according to a Latin square design; the washout period was 1 week. The analytical technique was a microbiological diffusion method. The pharmacokinetic parameters were calculated from the cumulative urinary excretion data and from a sigma-minus plot. The total amount of ofloxacin excreted in urine had a mean value of 163.59 +/- 22.13 mg when ofloxacin was administered alone, 152.41 +/- 18.76 mg when it was administered with Al3+, and 146.49 +/- 14.85 mg when it was administered with Fe2+. No statistically significant differences were found in the F values (fractions of dose absorbed) obtained with ofloxacin alone and ofloxacin plus Al3+ (P = 0.341). When ofloxacin alone was compared with joint administration with Fe2+ the value of F decreased 10.85%; this difference is statistically significant (P = 2.623 x 10(-2)). PMID:1759833

  6. Search for fullerenes and PAHs in the diffuse interstellar medium

    NASA Astrophysics Data System (ADS)

    Ehrenfreund, P.; Foing, B. H.

    1995-02-01

    Recent studies suggest carbon-containing molecules as the best candidates for carriers of the unidentified diffuse interstellar bands (DIBs). considering their abundance and ability to form stable bonds in interstellar space. We have searched for new DIBs in the near-IR and have detected two new diffuse bands that are consistent with laboratory measurements of C 60+ in a neon matrix. Criteria for this possible identification are discussed. From these observations and the DIB treasured absorption. we estimate that up to 0.9% of interstellar carbon could be in the form of C 60+ We also searched for poly cyclic aromatic hydrocarbon (PAH) canons and have derived corresponding limits for the presence of the coronene C 24H 12 and ovalene C 32H 14 cations in space. We have studied the ionization properties of these PAH cations, which could explain their selective destruction. From these results we discuss the role of fullerenes and PAHs as possible DIB carriers.

  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. A systematic determination of diffusion coefficients of trace elements in open and restricted diffusive layers used by the diffusive gradients in a thin film technique.

    PubMed

    Shiva, Amir Houshang; Teasdale, Peter R; Bennett, William W; Welsh, David T

    2015-08-12

    A systematic comparison of the diffusion coefficients of cations (Al, Cd, Co, Cu, Mn, Ni, Pb, Zn) and oxyanions (Al, As, Mo, Sb, V, W) in open (ODL) and restricted (RDL) diffusive layers used by the DGT technique was undertaken. Diffusion coefficients were measured using both the diffusion cell (Dcell) method at pH 4.00 and the DGT time-series (D(DGT)) method at pH 4.01 and 7.04 (pH 8.30 was used instead of 7.04 for Al) using the Chelex-Metsorb mixed binding layer. The performance of Chelex-Metsorb as a new DGT binding layer for Al uptake was also evaluated for the first time. Reasonable agreement was observed between D(cell) and D(DGT) measurements for both ODL and RDL, except for V and W. The ratios of D(cell)/D(DGT) for V of 0.44 and 0.39, and for W of 0.66 and 0.63 with ODL and RDL respectively, were much lower due to the formation of a high proportion of polyoxometalate species at the higher concentrations required with the D(cell) measurements. This is the first time that D values have been reported for several oxyanions using RDL. Except for Al at pH 8.30 with ODL, all D(DGT) measurements were retarded relative to diffusion coefficients in water (DW) for both diffusive hydrogels. Diffusion in RDL was further retarded compared with ODL, for all elements (0.66-0.78) with both methods. However, the degree of retardation observed changed for cations and anions at each pH. At pH 7.04 cations had a slightly higher D(DGT) and oxyanions had a slightly lower D(DGT) than at pH 4.01 for both ODL and RDL. It is proposed that this is due to partial formation of acrylic acid functional groups (pKa ≈4.5), which would be fully deprotonated at pH 7.04 (negative) and mostly protonated at pH 4.01 (neutral). As Al changes from being cationic at pH 4.01 to anionic at pH 8.30 the results were more complex.

  9. How We Think and Talk about Facilitation

    ERIC Educational Resources Information Center

    Kato, Fumitoshi

    2010-01-01

    Over the past few years, the notion of "facilitation" has been increasingly gaining attention and acceptance in Japan, especially in the context of education and training. Today, Japanese educators think and talk about facilitation, even if it is not yet clear what facilitation is. Interestingly enough, the term "facilitation" does not exist in…

  10. Diffusion bonding aeroengine components

    NASA Astrophysics Data System (ADS)

    Fitzpatrick, G. A.; Broughton, T.

    1988-10-01

    The use of diffusion bonding processes at Rolls-Royce for the manufacture of titanium-alloy aircraft engine components and structures is described. A liquid-phase diffusion bonding process called activated diffusion bonding has been developed for the manufacture of the hollow titanium wide chord fan blade. In addition, solid-state diffusion bonding is being used in the manufacture of hollow vane/blade airfoil constructions mainly in conjunction with superplastic forming and hot forming techniques.

  11. Updating applied diffusion models

    SciTech Connect

    Weil, J.C.

    1985-11-01

    Most diffusion models currently used in air quality applications are substantially out of date with understanding of turbulence and diffusion in the planetary boundary layer. Under a Cooperative Agreement with the Environmental Protection Agency, the American Meteorological Society organized a workshop to help improve the basis of such models, their physics and hopefuly their performance. Reviews and recommendations were made on models in three areas: diffusion in the convective boundary layer (CBL), diffusion in the stabe boundary layer (SBL), and model uncertainty.

  12. Numerical simulation of cesium and strontium migration through sodium bentonite altered by cation exchange with groundwater components

    SciTech Connect

    Jacobsen, J.S.; Carnahan, C.L.

    1988-10-01

    Numerical simulations have been used to investigate how spatial and temporal changes in the ion exchange properties of bentonite affect the migration of cationic fission products from high-level waste. Simulations in which fission products compete for exchange sites with ions present in groundwater diffusing into the bentonite are compared to simulations in which the exchange properties of bentonite are constant. 12 refs., 3 figs., 2 tabs.

  13. Characterization of perfluorinated cation-exchange membranes MF-4SC surface modified with halloysite nanotubes

    NASA Astrophysics Data System (ADS)

    Filippov, A.; Afonin, D.; Kononenko, N.; Shkirskaya, S.

    2015-10-01

    The electrical conductivity and diffusion permeability through perfluorinated cation-exchange membranes MF-4SC (Russian analog of the Nafion-type membrane), whose surface is modified by nanotubes of halloysite using short exposures of low temperature microwave plasma, are theoretically investigated using the Nernst-Planck approach. The method of quantitative evaluation of physicochemical parameters (individual and averaged diffusion coefficients and averaged distribution coefficients of ion pairs in the membrane) of the systems `electrolyte solution - bi-layer ion-exchange membrane - water/electrolyte solution', which was proposed by us earlier, is further developed. The aforementioned parameters of modified MF-4SC/halloysite membranes were found using the least squares method. For this purpose we used electrical conductivity as well as diffusion permeability data experimentally obtained for NaCl and HCl solutions of different concentration. A new model of bi-layer membrane system can be used for refining the calculated results by taking into account the difference between co- and counter-ion diffusivities inside the membrane layers. We showed that grafting the layer of halloysite nanotubes onto the membrane surface noticeably affects the exchange capacity as well as the structural and transport characteristics of the original perfluorinated membrane. In particular, such a membrane may show weak asymmetry of diffusion permeability when its position inside a measuring cell is changed. Hybrid MF-4SC/halloysite membranes can thus be productively used in fuel cells and catalysis.

  14. Detachment of surface membrane invagination systems by cationic amphiphilic drugs

    PubMed Central

    Osman, Sangar; Taylor, Kirk A.; Allcock, Natalie; Rainbow, Richard D.; Mahaut-Smith, Martyn P.

    2016-01-01

    Several cell types develop extensive plasma membrane invaginations to serve a specific physiological function. For example, the megakaryocyte demarcation membrane system (DMS) provides a membrane reserve for platelet production and muscle transverse (T) tubules facilitate excitation:contraction coupling. Using impermeant fluorescent indicators, capacitance measurements and electron microscopy, we show that multiple cationic amphiphilic drugs (CADs) cause complete separation of the DMS from the surface membrane in rat megakaryocytes. This includes the calmodulin inhibitor W-7, the phospholipase-C inhibitor U73122, and anti-psychotic phenothiazines. CADs also caused loss of T tubules in rat cardiac ventricular myocytes and the open canalicular system of human platelets. Anionic amphiphiles, U73343 (a less electrophilic U73122 analogue) and a range of kinase inhibitors were without effect on the DMS. CADs are known to accumulate in the inner leaflet of the cell membrane where they bind to anionic lipids, especially PI(4,5)P2. We therefore propose that surface detachment of membrane invaginations results from an ability of CADs to interfere with PI(4,5)P2 interactions with cytoskeletal or BAR domain proteins. This establishes a detubulating action of a large class of pharmaceutical compounds. PMID:26725955

  15. 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.

  16. 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

  17. Diffusion Strategy Guide.

    ERIC Educational Resources Information Center

    McCutcheon, James R.; Sanders, John R.

    A methodology is presented for planning and managing the spread of educational innovations. The first portion of the guide develops a theoretical framework for diffusion which summarizes and capitalizes on the latest marketing and on the latest marketing and diffusion research findings. Major stages in the diffusion paradigm discussed include…

  18. Reduce Confusion about Diffusion.

    ERIC Educational Resources Information Center

    Hebrank, Mary R.

    1997-01-01

    Presents activities that allow students to explore the fundamental but poorly understood concept of diffusion by appealing to their kinesthetic senses first, then challenging their analytical skills as they try to deduce the mathematical principle involved. Presents a computer simulation of diffusion and discusses diffusion's limitations and…

  19. Handbook on atmospheric diffusion

    SciTech Connect

    Hanna, S.R.; Briggs, G.A.; Hosker, R.P. Jr.

    1982-01-01

    Basic meteorological concepts are covered as well as plume rise, source effects, and diffusion models. Chapters are included on cooling tower plumes and urban diffusion. Suggestions are given for calculating diffusion in special situations, such as for instantaneous releases over complex terrain, over long distances, and during times when chemical reactions or dry or wet deposition are important. (PSB)

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

    SciTech Connect

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

    1994-06-01

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

  1. Sensing of biologically important cations such as Na(+), K(+), Ca(2+), Cu(2+), and Fe(3+) using magnetic nanoemulsions.

    PubMed

    Mahendran, V; Philip, John

    2013-04-01

    We report a simple approach to the ultrasensitive detection of biologically important metal ions using a magnetic nanoemulsion. The nanoemulsion used in our study was an oil-in-water emulsion droplet of average size ∼190 nm containing ferrimagnetic iron oxide nanoparticles of average size ∼10 nm. In a static magnetic field, the emulsion droplets self-assemble into a nanoarray with distinct interdroplet spacing. In the presence of cations in the solution, the nanofluid array shows a large blue shift in the diffracted Bragg peak and a visually perceivable color change due to changes in the electrical double layer upon the diffusion of cations. The colloidal force-distance measurements in the presence of cations show large variations at the onset of repulsion in the presence of cations. The sensor shows good selectivity to Na(+), K(+), Ca(2+), Cu(2+), and Fe(3+) ions and offers a rapid response compared to conventional techniques. This approach can be useful for the recognition of biologically important cations. PMID:23477486

  2. Na+ and Rb+ tracer diffusion in alkali halides

    NASA Astrophysics Data System (ADS)

    Beniere, F.; Sen, S. K.

    1991-11-01

    We have undertaken a fundamental study of heterodiffusion of foreign ions in pure single crystals. The present work describes the measurements of the diffusion coefficient of monovalent cations in some alkali halides, namely Na+ and Rb+ into KCl, KBr, NaI and KI. The priority is given to the super-accuracy of the experimental data. The target is to test the validity of the existing theories for calculating the enthalpy and entropy of migration.

  3. The role of helper lipids in cationic liposome-mediated gene transfer.

    PubMed Central

    Hui, S W; Langner, M; Zhao, Y L; Ross, P; Hurley, E; Chan, K

    1996-01-01

    -directed membrane motion, after their respective DNA:liposome complexes attached to cell surfaces by electrostatic means. Formation of granules on the cell surface facilitated and/or triggered endocytosis. Fusion between cationic liposomes and the cell membrane played a secondary role in determining transfection efficiency. Images FIGURE 1 FIGURE 9 FIGURE 10 PMID:8842198

  4. Two types of diffusions at the cathode/electrolyte interface in IT-SOFCs

    SciTech Connect

    Li Zhipeng; Mori, Toshiyuki; Auchterlonie, Graeme John; Zou Jin; Drennan, John

    2011-09-15

    Analytical transmission electron microscopy, in particular with the combination of energy dispersive X-ray spectroscopy (EDX) and electron energy-loss spectroscopy (EELS), has been performed to investigate the microstructure and microchemistry of the interfacial region between the cathode (La{sub 0.6}Sr{sub 0.4}Co{sub 0.8}Fe{sub 0.2}O{sub 3}, LSCF) and the electrolyte (Gd-doped ceria, GDC). Two types of diffusions, mutual diffusion between cathode and electrolyte as well as the diffusion along grain boundaries, have been clarified. These diffusions suggest that the chemical stability of LSCF and GDC are not as good as previously reported. The results are more noteworthy if we take into consideration the fact that such interdiffusions occur even during the sintering process of cell preparation. - Graphical Abstract: Two types of diffusions, the mutual diffusion and the diffusion along grain boundaries, occurred at the cathode/electrolyte interface of intermediate temperature solid state fuel cells, during cell preparation. The mutual diffusion is denoted by black arrows and the diffusion along grain boundaries assigned by pink arrows. Highlights: > All the cations in cathode (LSCF) and electrolyte (GDC) can mutually diffuse into each other. > Diffusing elements will segregate at grain boundaries or triple junctions around the cathode/electrolyte interface. > Two types of diffusions, the mutual diffusion and diffusion along grain boundaries, have been clarified thereafter.

  5. Nonlinearity of cationic aromatic amine sorption to aluminosilicates and soils: role of intermolecular cation-π interactions.

    PubMed

    Vasudevan, Dharni; Arey, Teresa A; Dickstein, Daniel R; Newman, Mark H; Zhang, Tina Y; Kinnear, Heather M; Bader, Mohammad M

    2013-12-17

    Through the study of substituted anilines and benzylamines, we demonstrated that cooperative cation-π, π-π, and van der Waals interactions can increase aromatic cationic amine sorption to Na/Ca-montmorillonite well beyond the extent expected by cation exchange alone. Cationic amines exhibiting cooperative interactions displayed nonlinear S-shaped isotherms and increased affinity for the sorbent at low surface coverage; parallel cation exchange and cooperative interactions were noted above a sorption threshold of 0.3-2.3% of exchange sites occupied. Our experiments revealed the predominance of intermolecular cation-π interactions, which occurred between the π system of a compound retained on the surface via cation exchange and the cationic amine group of an adjacent molecule. Compounds with greater amine charge/area and electron-donating substituents that allowed for greater electron density at the center of the aromatic ring showed a greater potential for cation-π interactions on montmorillonite surfaces. However, benzylamine sorption to nine soils, at charge loadings comparable to the experiments with montmorillonite, revealed no significant cooperative interactions. It appears that cation-π interactions may be likely in soils with exceptionally high cation exchange capacities (>0.7 mol charge/kg) and low organic matter contents, abundant in montmorillonite and other expanding clay minerals.

  6. Stochastic facilitation in the brain?

    NASA Astrophysics Data System (ADS)

    Ward, Lawrence M.; Greenwood, Priscilla E.

    2016-05-01

    We describe the context for three unsolved problems of noise in the brain as well as provide some new results relevant to one of them. The problems are: are neural oscillations better described as noisy limit cycles or as noise-driven quasicycles, does noise facilitate synchronization and information transmission in the brain, and do noise-driven spatial patterns (quasipatterns) coexist with noise-driven quasicycles in the brain? We provide a few new results indicating that, in models at least, spatial quasipatterns of quasicycles can occur, and resemble patterns observed in other areas, such as predator-prey systems and chemical reactions.

  7. Simulated Transport of Three Cations Through Porous Media: Effect of Different Approaches to Modeling Cation Exchange Reactions

    NASA Astrophysics Data System (ADS)

    Grant, S. A.; Mansell, R. S.; Bloom, S. A.; Rhue, R. D.

    1995-01-01

    Batch cation exchange and column experiments were conducted to evaluate selectivity coefficients which have been suggested for describing cation exchange reactions in solute transport models. Vanselow selectivity coefficients were calculated for cation exchange equilibria with a cation resin and for equilibria reported in the literature with a Yolo loam soil. Experimental column data were compared with data from simulations generated by a numerical solute transport model to evaluate Vanselow, Gaines-Thomas, and statistical thermodynamic selectivity coefficients. With the cation resin, the statistical thermodynamic selectivity coefficient gave the most reliable estimate of column effluent cation concentrations. In a column packed with the Yolo loam soil, the Vanselow selectivity coefficient gave the most accurate prediction of column response. Use of variable (as opposed to fixed) Vanselow selectivity coefficients gave more accurate predictions of column experiments. The use of ternary cation exchange data did not improve predictions of column response.

  8. Oxidation of thioanisole and p-methoxythioanisole by lignin peroxidase: kinetic evidence of a direct reaction between compound II and a radical cation.

    PubMed Central

    Brück, Thomas B; Gerini, Maria Francesca; Baciocchi, Enrico; Harvey, Patricia J

    2003-01-01

    The reaction of H2O2 with thioanisole and p-methoxythioanisole catalysed by lignin peroxidase from Phanerochaete chrysosporium has been studied spectrophotometrically under turnover and single turnover conditions with a stopped-flow apparatus. Pre-formed lignin peroxidase compounds I and II are each able to react with the sulphides to form a sulphide radical cation. The radical cation is then converted into the sulphoxide either by reaction with the medium or by reaction with compound II. This is the first report of a direct reaction between compound II and the substrate radical cation. With thioanisole, significant enantiomeric selectivity and high oxygen incorporation in the sulphoxide are obtained because compound II is preferentially reduced by the enzyme-bound thioanisole radical cation compared with the neutral substrate. By contrast, with p-methoxythioanisole, the data imply formation of an intermediate ternary complex comprising compound II, radical cation and neutral substrate, such that a chain of electron transfer reactions starting from neutral molecule and progressing to oxidized haem via substrate radical cation is facilitated, yielding the native enzyme and two molecules of p-methoxythioanisole radical cation as products. The reactions of compounds I and II with sulphides imply flexing of the apoprotein moiety during catalysis. PMID:12803544

  9. 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.

  10. 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.

  11. Development of cationic nanocrystals for ocular delivery.

    PubMed

    Romero, Gregori B; Keck, Cornelia M; Müller, Rainer H; Bou-Chacra, Nadia A

    2016-10-01

    A cationic nanocrystal formulation containing dexamethasone acetate nanocrystals (0.05%) and polymyxin B (0.10%) for ophthalmic application was produced using a self-developed small scale method for wet bead milling. The formulation developed offers the advantage of increased saturation solubility of the drug (due to the nano-size of the crystals) and increased residence time in the eye (due to small size and increased mucoadhesion by the cationic charge) resulting ultimately in potential increased bioavailability. Characterization of the nanosuspensions by photon correlation spectroscopy (PCS) and transmission electron microscopy showed that the production method was successful in achieving dexamethasone crystals in the range of about 200-250nm. The physical stabilization of the nanocrystals and generation of the positive charge were realized by using cetylpyridinium chloride (CPC) and benzalkonium chloride (BAC) at the concentration of 0.01%. In contrast to other cationic excipients, they are regulatorily accepted due to their use as preservatives. The drug polymyxin B also contributed to the positive charge. Positive zeta potentials in the range +20 to +30mV were achieved. Isotonicity was adjusted using NaCl and non-ionic excipients (glycerol, sorbitol, dextrose). Physical and chemical stabilities were monitored for a period of 6months at room temperature, 5°C and 40°C. Particle size of the bulk population assessed by PCS remained practically unchanged over 6months of storage for the various formulations without isotonicity agents, and for the CPC-containing formulations with non-ionic isotonicity excipients. The chemical content also proved stable after 6months for all 3 temperatures evaluated. In vitro investigation of mucoadhesion was tested using mucin solutions at different concentrations, and the generated negative zeta potential was used as a measure of the interaction. The zeta potential reversed to about -15mV, indicating distinct interaction. The

  12. Positive Emotion Facilitates Audiovisual Binding

    PubMed Central

    Kitamura, Miho S.; Watanabe, Katsumi; Kitagawa, Norimichi

    2016-01-01

    It has been shown that positive emotions can facilitate integrative and associative information processing in cognitive functions. The present study examined whether emotions in observers can also enhance perceptual integrative processes. We tested 125 participants in total for revealing the effects of emotional states and traits in observers on the multisensory binding between auditory and visual signals. Participants in Experiment 1 observed two identical visual disks moving toward each other, coinciding, and moving away, presented with a brief sound. We found that for participants with lower depressive tendency, induced happy moods increased the width of the temporal binding window of the sound-induced bounce percept in the stream/bounce display, while no effect was found for the participants with higher depressive tendency. In contrast, no effect of mood was observed for a simple audiovisual simultaneity discrimination task in Experiment 2. These results provide the first empirical evidence of a dependency of multisensory binding upon emotional states and traits, revealing that positive emotions can facilitate the multisensory binding processes at a perceptual level. PMID:26834585

  13. No facilitator required for membrane transport of hydrogen sulfide

    PubMed Central

    Mathai, John C.; Missner, Andreas; Kügler, Philipp; Saparov, Sapar M.; Zeidel, Mark L.; Lee, John K.; Pohl, Peter

    2009-01-01

    Hydrogen sulfide (H2S) has emerged as a new and important member in the group of gaseous signaling molecules. However, the molecular transport mechanism has not yet been identified. Because of structural similarities with H2O, it was hypothesized that aquaporins may facilitate H2S transport across cell membranes. We tested this hypothesis by reconstituting the archeal aquaporin AfAQP from sulfide reducing bacteria Archaeoglobus fulgidus into planar membranes and by monitoring the resulting facilitation of osmotic water flow and H2S flux. To measure H2O and H2S fluxes, respectively, sodium ion dilution and buffer acidification by proton release (H2S ⇆ H+ + HS−) were recorded in the immediate membrane vicinity. Both sodium ion concentration and pH were measured by scanning ion-selective microelectrodes. A lower limit of lipid bilayer permeability to H2S, PM,H2S ≥ 0.5 ± 0.4 cm/s was calculated by numerically solving the complete system of differential reaction diffusion equations and fitting the theoretical pH distribution to experimental pH profiles. Even though reconstitution of AfAQP significantly increased water permeability through planar lipid bilayers, PM,H2S remained unchanged. These results indicate that lipid membranes may well act as a barrier to water transport although they do not oppose a significant resistance to H2S diffusion. The fact that cholesterol and sphingomyelin reconstitution did not turn these membranes into an H2S barrier indicates that H2S transport through epithelial barriers, endothelial barriers, and membrane rafts also occurs by simple diffusion and does not require facilitation by membrane channels. PMID:19805349

  14. High-speed simultaneous ion-exclusion/cation-exchange chromatography of anions and cations on a weakly acidic cation-exchange resin column.

    PubMed

    Mori, Masanobu; Tanaka, Kazuhiko; Helaleh, Murad I H; Xu, Qun; Ikedo, Mikaru; Ogura, Yutaka; Sato, Shinji; Hu, Wenzhi; Hasebe, Kiyoshi; Haddad, Paul R

    2003-05-16

    The simultaneous ion-exclusion/cation-exchange separation column packed with a polymethacrylate-based weakly acidic cation-exchange resin of 3 microm particle size was used to achieve the simultaneous high-speed separation of anions and cations (Cl(-), NO3(-), SO4(2-), Na(+), K(+), NH4(+), Ca(2+) and Mg(2+)) commonly found in environmental samples. The high-speed simultaneous separation is based on a combination of the ion-exclusion mechanism for the anions and the cation-exchange mechanism for cations. The complete separation of the anions and cations was achieved in 5 min by elution with 15 mM tartaric acid-2.5 mM 18-crown-6 at a flow-rate of 1.5 ml/min. Detection limits at S/N=3 ranged from 0.36 to 0.68 microM for anions and 0.63-0.99 microM for cations. This method has been applied to the simultaneous determination of anions and cations in several environmental waters with satisfactory results.

  15. Electron spin resonance spectroscopic studies of radical cation reactions

    SciTech Connect

    Dai, S.

    1990-01-01

    A spin Hamiltonian suitable for theoretical analyses of ESR spectra is derived using the general effective Hamiltonian theory in the usual Schroedinger 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 are derived using 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 synsesquinorbornene oxide have been characterized by ESR spectroscopy in the CFCl[sub 3] matrix at low temperature. 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 the 3-iminiopropyl distonic species(3-iminium-1-propyl radical). The nucleophilic endocylization 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-hexdiyne have resulted in characterization the 1,5-hexadiyne radical cation isomerizing to the 1,2,4,5-hexatetraene radical cation. The symmetric (C[sub 2v]) bicyclo[3.3.0]-octa-2,6-diene-4,8-diyl(a bridged 1,4-bishomobenzene species) radical cation is produced by the radiolytic oxidation of semibullvalene in Freon matrices. The ring-opening 3,4-dimethylenecyclobutene radical cation to 1,2,4,5-hexatetraene radical cation was observed in the photolysis of 3,4-dimethylenecyclobutene radical cation. The cyclooctatetraene radical cation generated by radiolytic oxidation photoisomerizes to bicyclo[3.3.0]octa-2,6-diene-4,8-diyl radical cation.

  16. Understanding heat facilitated drug transport across human epidermis.

    PubMed

    Wood, D G; Brown, M B; Jones, S A

    2012-08-01

    The application of moderate heat is a safe and effective means to increase drug transport across human skin. However, the cascade of events that follows the exposure of a topical skin formulation to a heating source is not well understood. The aim of this study was to elucidate how three potential rate limiting stages in the drug transport process; formulation release, drug partitioning and epidermal diffusion, responded to changes in local temperature using the model drug lidocaine. Release from the formulation measured using regenerated cellulose membrane was shown to be driven by drug diffusion in the vehicle; it responded linearly when the local temperature was changed (21.6 μg/cm(2)/h for every 1 °C rise) and displayed no measurable partitioning of lidocaine into RCM. Once the drug was within the human epidermis, the structural changes of the barrier controlled its transport. The apparent lidocaine diffusion coefficient through silicone membrane increased from 6.52 to 8.43 × 10(-4) over the 32-45 °C temperature range, but it increased from 7.74 × 10(-5)cm(2)h(-1) to 4.8 × 10(-4)cm(2)h(-1) in the human epidermis. In the absence of large increases in drug partitioning, fluidisation of the lipids in the upper layers of the epidermis at 37-45 °C was shown to facilitate lidocaine diffusion which for human skin transport was the rate limiting process.

  17. Transport by Collective Flagellar Beating Facilitates Evolutionary Transitions to Multicellularity

    NASA Astrophysics Data System (ADS)

    Short, Martin; Powers, Thomas

    2005-11-01

    A central problem underlying the evolution from single cells to multicellular organisms is the relationship between metabolic requirements and environmental metabolite exchange with increasing size. For organisms that form spherical colonies such as the volvocalean green algae, there is a bottleneck if diffusion alone governs nutrient uptake as they increase in size, for the diffusive flux is linear in the radius while the requirements of surface somatic cells grow quadratically. Using Volvox as a model organism, we examine experimentally and theoretically the role that advection of fluid by surface flagella plays in enhancing nutrient uptake. We show that the fluid flow driven by the coordinated beating of those flagella produces a boundary layer in the concentration of a diffusing solute which renders the metabolite exchange rate quadratic in the colony radius. This bypasses the diffusive bottleneck, facilitating evolutionary transitions to multicellularity which may be driven by other environmental factors. These results suggest that flagella may have evolved not only for motility, but also to enhance metabolite exchange.

  18. Treatment of boundary conditions in through-diffusion: A case study of (85)Sr(2+) diffusion in compacted illite.

    PubMed

    Glaus, M A; Aertsens, M; Maes, N; Van Laer, L; Van Loon, L R

    2015-01-01

    Valuable techniques to measure effective diffusion coefficients in porous media are an indispensable prerequisite for a proper understanding of the migration of chemical-toxic and radioactive micropollutants in the subsurface and geosphere. The present article discusses possible pitfalls and difficulties in the classical through-diffusion technique applied to situations where large diffusive fluxes of cations in compacted clay minerals or clay rocks occur. The results obtained from a benchmark study, in which the diffusion of (85)Sr(2+) tracer in compacted illite has been studied using different experimental techniques, are presented. It is shown that these techniques may yield valuable results provided that an appropriate model is used for numerical simulations. It is further shown that effective diffusion coefficients may be systematically underestimated when the concentration at the downstream boundary is not taken adequately into account in modelling, even for very low concentrations. A criterion is derived for quasi steady-state situations, by which it can be decided whether the simplifying assumption of a zero-concentration at the downstream boundary in through-diffusion is justified or not. The application of the criterion requires, however, knowledge of the effective diffusion coefficient of the clay sample. Such knowledge is often absent or only approximately available during the planning phase of a diffusion experiment.

  19. Treatment of boundary conditions in through-diffusion: A case study of (85)Sr(2+) diffusion in compacted illite.

    PubMed

    Glaus, M A; Aertsens, M; Maes, N; Van Laer, L; Van Loon, L R

    2015-01-01

    Valuable techniques to measure effective diffusion coefficients in porous media are an indispensable prerequisite for a proper understanding of the migration of chemical-toxic and radioactive micropollutants in the subsurface and geosphere. The present article discusses possible pitfalls and difficulties in the classical through-diffusion technique applied to situations where large diffusive fluxes of cations in compacted clay minerals or clay rocks occur. The results obtained from a benchmark study, in which the diffusion of (85)Sr(2+) tracer in compacted illite has been studied using different experimental techniques, are presented. It is shown that these techniques may yield valuable results provided that an appropriate model is used for numerical simulations. It is further shown that effective diffusion coefficients may be systematically underestimated when the concentration at the downstream boundary is not taken adequately into account in modelling, even for very low concentrations. A criterion is derived for quasi steady-state situations, by which it can be decided whether the simplifying assumption of a zero-concentration at the downstream boundary in through-diffusion is justified or not. The application of the criterion requires, however, knowledge of the effective diffusion coefficient of the clay sample. Such knowledge is often absent or only approximately available during the planning phase of a diffusion experiment. PMID:26004771

  20. Treatment of boundary conditions in through-diffusion: A case study of 85Sr2 + diffusion in compacted illite

    NASA Astrophysics Data System (ADS)

    Glaus, M. A.; Aertsens, M.; Maes, N.; Van Laer, L.; Van Loon, L. R.

    2015-06-01

    Valuable techniques to measure effective diffusion coefficients in porous media are an indispensable prerequisite for a proper understanding of the migration of chemical-toxic and radioactive micropollutants in the subsurface and geosphere. The present article discusses possible pitfalls and difficulties in the classical through-diffusion technique applied to situations where large diffusive fluxes of cations in compacted clay minerals or clay rocks occur. The results obtained from a benchmark study, in which the diffusion of 85Sr2 + tracer in compacted illite has been studied using different experimental techniques, are presented. It is shown that these techniques may yield valuable results provided that an appropriate model is used for numerical simulations. It is further shown that effective diffusion coefficients may be systematically underestimated when the concentration at the downstream boundary is not taken adequately into account in modelling, even for very low concentrations. A criterion is derived for quasi steady-state situations, by which it can be decided whether the simplifying assumption of a zero-concentration at the downstream boundary in through-diffusion is justified or not. The application of the criterion requires, however, knowledge of the effective diffusion coefficient of the clay sample. Such knowledge is often absent or only approximately available during the planning phase of a diffusion experiment.

  1. Stabilization of the veratryl alcohol cation radical by lignin peroxidase.

    PubMed

    Khindaria, A; Yamazaki, I; Aust, S D

    1996-05-21

    Lignin peroxidase (LiP) catalyzes the H2O2-dependent oxidation of veratryl alcohol (VA) to veratryl aldehyde, with the enzyme-bound veratryl alcohol cation radical (VA.+) as an intermediate [Khindaria et al. (1995) Biochemistry 34, 16860-16869]. The decay constant we observed for the enzyme generated cation radical did not agree with the decay constant in the literature [Candeias and Harvey (1995) J. Biol. Chem. 270, 16745-16748] for the chemically generated radical. Moreover, we have found that the chemically generated VA.+ formed by oxidation of VA by Ce(IV) decayed rapidly with a first-order mechanism in air- or oxygen-saturated solutions, with a decay constant of 1.2 x 10(3) s-1, and with a second-order mechanism in argon-saturated solution. The first-order decay constant was pH- independent suggesting that the rate-limiting step in the decay was deprotonation. When VA.+ was generated by oxidation with LiP the decay also occurred with a first-order mechanism but was much slower, 1.85 s-1, and was the same in both oxygen- and argon-saturated reaction mixtures. However, when the enzymatic reaction mixture was acid-quenched the decay constant of VA.+ was close to the one obtained in the Ce(IV) oxidation system, 9.7 x 10(2) s-1. This strongly suggested that the LiP-bound VA.+ was stabilized and decayed more slowly than free VA.+. We propose that the stabilization of VA.+ may be due to the acidic microenvironment in the enzyme active site, which prevents deprotonation of the radical and subsequent reaction with oxygen. We have also obtained reversible redox potential of VA.+/VA couple using cyclic voltammetery. Due to the instability of VA.+ in aqueous solution the reversible redox potential was measured in acetone, and was 1.36 V vs normal hydrogen electrode. Our data allow us to propose that enzymatically generated VA.+ can act as a redox mediator but not as a diffusible oxidant for LiP-catalyzed lignin or pollutant degradation.

  2. 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

  3. 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

  4. An optical spectrum of a large isolated gas-phase PAH cation: C78H26+

    NASA Astrophysics Data System (ADS)

    Zhen, Junfeng; Mulas, Giacomo; Bonnamy, Anthony; Joblin, Christine

    2016-03-01

    A gas-phase optical spectrum of a large polycyclic aromatic hydrocarbon (PAH) cation - C78H26+ - in the 410 -610 nm range is presented. This large all-benzenoid PAH should be large enough to be stable with respect to photodissociation in the harsh conditions prevailing in the interstellar medium (ISM). The spectrum is obtained via multi-photon dissociation (MPD) spectroscopy of cationic C78H26 stored in the Fourier Transform Ion Cyclotron Resonance (FT-ICR) cell of the PIRENEA setup using the radiation from a mid-band optical parametric oscillator (OPO) laser. The experimental spectrum shows two main absorption peaks at 431 nm and 516 nm, in good agreement with a theoretical spectrum computed via time-dependent density functional theory (TD-DFT). DFT calculations indicate that the equilibrium geometry, with the absolute minimum energy, is of lowered, nonplanar C2 symmetry instead of the more symmetric planar D2h symmetry that is usually the minimum for similar PAHs of smaller size. This kind of slightly broken symmetry could produce some of the fine structure observed in some diffuse interstellar bands (DIBs). It can also favor the folding of C78H26+ fragments and ultimately the formation of fullerenes. This study opens up the possibility to identify the most promising candidates for DIBs amongst large cationic PAHs.

  5. An optical spectrum of a large isolated gas-phase PAH cation: C78H26+

    PubMed Central

    Zhen, Junfeng; Mulas, Giacomo; Bonnamy, Anthony; Joblin, Christine

    2016-01-01

    A gas-phase optical spectrum of a large polycyclic aromatic hydrocarbon (PAH) cation - C78H26+- in the 410-610 nm range is presented. This large all-benzenoid PAH should be large enough to be stable with respect to photodissociation in the harsh conditions prevailing in the interstellar medium (ISM). The spectrum is obtained via multi-photon dissociation (MPD) spectroscopy of cationic C78H26 stored in the Fourier Transform Ion Cyclotron Resonance (FT-ICR) cell using the radiation from a mid-band optical parametric oscillator (OPO) laser. The experimental spectrum shows two main absorption peaks at 431 nm and 516 nm, in good agreement with a theoretical spectrum computed via time-dependent density functional theory (TD-DFT). DFT calculations indicate that the equilibrium geometry, with the absolute minimum energy, is of lowered, nonplanar C2 symmetry instead of the more symmetric planar D2h symmetry that is usually the minimum for similar PAHs of smaller size. This kind of slightly broken symmetry could produce some of the fine structure observed in some diffuse interstellar bands (DIBs). It can also favor the folding of C78H26+ fragments and ultimately the formation of fullerenes. This study opens up the possibility to identify the most promising candidates for DIBs amongst large cationic PAHs. PMID:26942230

  6. Human proximal tubule epithelial cells cultured on hollow fibers: living membranes that actively transport organic cations

    PubMed Central

    Jansen, J.; De Napoli, I. E; Fedecostante, M.; Schophuizen, C. M. S.; Chevtchik, N. V.; Wilmer, M. J.; van Asbeck, A. H.; Croes, H. J.; Pertijs, J. C.; Wetzels, J. F. M.; Hilbrands, L. B.; van den Heuvel, L. P.; Hoenderop, J. G.; Stamatialis, D.; Masereeuw, R.

    2015-01-01

    The bioartificial kidney (BAK) aims at improving dialysis by developing ‘living membranes’ for cells-aided removal of uremic metabolites. Here, unique human conditionally immortalized proximal tubule epithelial cell (ciPTEC) monolayers were cultured on biofunctionalized MicroPES (polyethersulfone) hollow fiber membranes (HFM) and functionally tested using microfluidics. Tight monolayer formation was demonstrated by abundant zonula occludens-1 (ZO-1) protein expression along the tight junctions of matured ciPTEC on HFM. A clear barrier function of the monolayer was confirmed by limited diffusion of FITC-inulin. The activity of the organic cation transporter 2 (OCT2) in ciPTEC was evaluated in real-time using a perfusion system by confocal microscopy using 4-(4-(dimethylamino)styryl)-N-methylpyridinium iodide (ASP+) as a fluorescent substrate. Initial ASP+ uptake was inhibited by a cationic uremic metabolites mixture and by the histamine H2-receptor antagonist, cimetidine. In conclusion, a ‘living membrane’ of renal epithelial cells on MicroPES HFM with demonstrated active organic cation transport was successfully established as a first step in BAK engineering. PMID:26567716

  7. Human proximal tubule epithelial cells cultured on hollow fibers: living membranes that actively transport organic cations.

    PubMed

    Jansen, J; De Napoli, I E; Fedecostante, M; Schophuizen, C M S; Chevtchik, N V; Wilmer, M J; van Asbeck, A H; Croes, H J; Pertijs, J C; Wetzels, J F M; Hilbrands, L B; van den Heuvel, L P; Hoenderop, J G; Stamatialis, D; Masereeuw, R

    2015-11-16

    The bioartificial kidney (BAK) aims at improving dialysis by developing 'living membranes' for cells-aided removal of uremic metabolites. Here, unique human conditionally immortalized proximal tubule epithelial cell (ciPTEC) monolayers were cultured on biofunctionalized MicroPES (polyethersulfone) hollow fiber membranes (HFM) and functionally tested using microfluidics. Tight monolayer formation was demonstrated by abundant zonula occludens-1 (ZO-1) protein expression along the tight junctions of matured ciPTEC on HFM. A clear barrier function of the monolayer was confirmed by limited diffusion of FITC-inulin. The activity of the organic cation transporter 2 (OCT2) in ciPTEC was evaluated in real-time using a perfusion system by confocal microscopy using 4-(4-(dimethylamino)styryl)-N-methylpyridinium iodide (ASP(+)) as a fluorescent substrate. Initial ASP(+) uptake was inhibited by a cationic uremic metabolites mixture and by the histamine H2-receptor antagonist, cimetidine. In conclusion, a 'living membrane' of renal epithelial cells on MicroPES HFM with demonstrated active organic cation transport was successfully established as a first step in BAK engineering.

  8. Effects of ionic liquids on cation dynamics in amorphous polyethylene oxide electrolytes

    SciTech Connect

    Chattoraj, Joyjit Diddens, Diddo; Heuer, Andreas

    2014-01-14

    We perform extensive molecular dynamics simulations of a poly(ethylene oxide)-based polymer electrolyte material containing lithium bis(trifluoromethanesulfonyl)imide salt for a wide temperature regime above and below the experimental crystallization temperature with and without N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide ionic liquid (IL). The impact of the IL-concentration on the cation dynamics is studied. The increase of the cation mobility upon addition of IL is significant but temperature-independent. This can be related to distinct variations of the underlying transport properties as expressed within the previously introduced transport model of polymer electrolytes. Even for the largest IL concentration the transport model perfectly predicts the non-trivial time-dependence of the cationic mean square displacement for all temperatures. Finally, we compare our numerical and theoretical findings with the results of recent nuclear magnetic resonance experiments. In this way we can exclusively relate the strong experimentally observed dependence of the low-temperature Li-diffusivity on the IL concentration to the impact of IL on crystallization.

  9. 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

  10. 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

  11. 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.

  12. Transition-Metal Hydride Radical Cations.

    PubMed

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

    2016-08-10

    Transition-metal hydride radical cations (TMHRCs) are involved in a variety of chemical and biochemical reactions, making a more thorough understanding of their properties essential for explaining observed reactivity and for the eventual development of new applications. Generally, these species may be treated as the ones formed by one-electron oxidation of diamagnetic analogues that are neutral or cationic. Despite the importance of TMHRCs, the generally sensitive nature of these complexes has hindered their development. However, over the last four decades, many more TMHRCs have been synthesized, characterized, isolated, or hypothesized as reaction intermediates. This comprehensive review focuses on experimental studies of TMHRCs reported through the year 2014, with an emphasis on isolated and observed species. The methods used for the generation or synthesis of TMHRCs are surveyed, followed by a discussion about the stability of these complexes. The fundamental properties of TMHRCs, especially those pertaining to the M-H bond, are described, followed by a detailed treatment of decomposition pathways. Finally, reactions involving TMHRCs as intermediates are described. PMID:26828562

  13. Electrostatics of DNA complexes with cationic lipids

    NASA Astrophysics Data System (ADS)

    Cherstvy, Andrey

    2007-03-01

    We present the exact solutions of the linear Poisson-Boltzmann theory for several problems relevant to electrostatics of DNA complexes with cationic lipids. We calculate the electrostatic potential and energy for lamellar and inverted hexagonal phases, concentrating on the effects of water-membrane dielectric boundaries. Our results for the complex energy agree qualitatively well with the known numerical solutions of the nonlinear Poisson-Boltzmann equation. Using the solution for the lamellar phase, we calculate its compressibility modulus and compare our findings with experimental data available suggesting a new scaling dependence on DNA-DNA separations in the complex. Also, we treat analytically charge-charge electrostatic interactions across, along, and in between two low-dielectric membranes. We obtain an estimate for the strength of electrostatic interactions of 1D DNA smectic layers across a lipid membrane. We discuss also some aspects of 2D DNA condensation and DNA-DNA attraction in DNA-lipid lamellar phase in the presence of di- and tri-valent cations and analyze the equilibrium intermolecular separations using the recently developed theory of electrostatic interactions of DNA helical charge motifs.

  14. 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.

  15. Cation adsorption on manganese dioxide impregnated fibers

    SciTech Connect

    Fisher, S. ); Stahel, E.P. )

    1992-12-01

    Complete removal of radioactive cations by standard mixed bed ion exchange resins is sometimes not achieved in liquid radwaste systems. Based on a literature survey, acrylic fibers impregnated with manganese dioxide were chosen as a media warranting study of their ability to adsorb the cations present in radwaste systems in the hope of improving performance of such treatment processes. A system to produce impregnated fiber with a heavy MnO[sub 2] loading was designed, constructed, and operated. The system produced fiber at an average fiber loading of 22.5 percent MnO[sub 2] by weight. Leaching tests made on the MnO[sub 2] fiber exhibited no signs of soluble manganese, insoluble MnO[sub 2], acrylonitrile leaching or fiber loss. Laboratory testing has been performed on the adsorption of calcium, cadmium, cesium, cobalt, iron, and manganese on MnO[sub 2] impregnated fiber. Removal of metals from solution was measured at levels specific for each metal tested. The removal efficiency when they were present in combination was also evaluated.

  16. Biomimetic CO2 Sequestration: Cation Sources

    NASA Astrophysics Data System (ADS)

    Bond, G. M.; Stringer, J.; Medina, M.; McPherson, B.; Wellman, T.; Lichtner, P. C.; Abel, A.

    2001-12-01

    Conversion of CO2 to solid carbonates offers the possibility of a safe, stable product for long-term carbon sequestration. Naturally occurring carbonate minerals already comprise a massive carbon reservoir that has existed for millions of years. Large quantities of these carbonate minerals are of biogenic origin. We have demonstrated proof of principle for a novel biomimetic approach to carbon sequestration, which uses a natural catalyst, the enzyme carbonic anhydrase, to accelerate the formation of bicarbonate ions in aqueous solution. In the presence of suitable cations, this can then be precipitated out in carbonate form. One of the issues we are now addressing is the selection of suitable sources of cations. Along with seawater, and waste brines from desalination operations, brines from deep saline aquifers offer an attractive possibility. In this context, it is important to understand the effects of brine flow on geologic media, both during brine extraction and during possible reinjection of bicarbonate-enriched brines. We have used numerical simulations to evaluate and compare the effects of supercritical CO2 flow to the effects of bicarbonate solution flow on geologic media. Specifically, we examined diagenetic changes and time-scales of these changes associated with flow of the two different fluids. For these simulations we assembled and applied a model of reactive transport, including coupled groundwater flow, heat flow, and relevant geochemical reactions. Simulations have been conducted for laboratory-scale models, with the intention that these results will be used for calibration of and upscaling to larger-scale hydrogeologic models.

  17. 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.

  18. Transition-Metal Hydride Radical Cations.

    PubMed

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

    2016-08-10

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

  19. 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

  20. Tobacco use prevention and health facilitator effectiveness.

    PubMed

    Young, R L; Elder, J P; Green, M; de Moor, C; Wildey, M B

    1988-11-01

    Tobacco prevention programs often use peers to teach refusal skills to other adolescents. College undergraduate health facilitators delivered a tobacco prevention intervention to sixth and seventh grade students in six schools. Outside observers evaluated facilitators in seven categories: being prepared, maintaining class control, keeping students' attention, encouraging participation, communication, relating to students, and working well in a team. Facilitators were rated highly in all categories. Higher rated health facilitators had more effect in reducing tobacco use than poorly rated facilitators. Facilitators who worked well in a team, related well to students, and were well-prepared were especially effective in positively influencing program outcomes.

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

    SciTech Connect

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

    2007-06-11

    Carotenoids, intrinsic components of reaction centers and pigment-protein complexes in photosynthetic membranes, play a photoprotective role and serve as a secondary electron donor. Before optimum use of carotenoids can be made in artificial photosynthetic systems, their robust nature in living materials requires extensive characterization of their electron transfer, radical trapping ability, stability, structure in and on various hosts, and photochemical behavior. Pulsed ENDOR and 2D-HYSCORE studies combined with DFT calculations reveal that photo-oxidation of natural zeaxanthin (I) and violaxanthin (II) on silica-alumina produces not only the carotenoid radical cations (Car•+) but also neutral radicals (#Car•) by proton loss from the methyl groups at positions 5 or 5', and possibly 9 or 9' and 13 or 13'. Notably, the proton loss favored in I at the 5 position by DFT calculations, is unfavorable in II due to the epoxide at the 5, 6 position. DFT calculations predict the isotropic methyl proton couplings of 8-10 MHz for Car•+ which agree with the ENDOR for carotenoid α-conjugated radical cations. Large α-proton hyperfine coupling constants (>10 MHz) determined from HYSCORE are assigned from the DFT calculations to neutral carotenoid radicals. Proton loss upon photolysis was also examined as a function of carotenoid polarity [Lycopene (III) versus 8'-apo-β-caroten-8'-al (IV)]; hydrogen bonding [Lutein (V) versus III]; host [silica-alumina versus MCM-41 molecular sieve]; and substituted metal in MCM-41. Loss of H+ from the 5(5'), 9(9') or 13(13') methyl positions has importance in photoprotection. Photoprotection involves nonphotochemical quenching (NPQ) in which 1Ch1* decays via energy transfer to the carotenoid which returns to the ground state by thermal dissipation; or via electron transfer to form a charge transfer state (I •+…Chl•-), lower in energy than 1Chl*. Formation of I •+ results in bond lengthening, a mechanism for nonradiative energy

  2. The Influence of Facilitator and Facilitation Characteristics on Participants' Ratings of Stepfamily Education

    ERIC Educational Resources Information Center

    Higginbotham, Brian J.; Myler, Cory

    2010-01-01

    We examine the relative importance of facilitator and facilitation characteristics on participant ratings of a stepfamily education program. Data from 48 facilitators and 598 participants suggest that quality facilitation is more meaningful to participants than whether facilitators have comparable demographic characteristics or life experiences.…

  3. Guanidinium Pairing Facilitates Membrane Translocation.

    PubMed

    Allolio, Christoph; Baxova, Katarina; Vazdar, Mario; Jungwirth, Pavel

    2016-01-14

    Ab initio free energy calculations of guanidinium pairing in aqueous solution confirm the counterintuitive conjecture that the like-charge ion pair is thermodynamically stable. Transferring the guanidinium pair to the inside of a POPC lipid bilayer, like-charge ion pairing is found to occur also inside the membrane defect. It is found to contribute to the nonadditivity of ion transfer, thereby facilitating the presence of ions inside the bilayer. The effect is quantified by free energy decomposition and comparison with ammonium ions, which do not form a stable pair. The presence of two charges inside the center of the bilayer leads to the formation of a pore. Potential consequences for cell penetrating peptides and ion conduction are drawn.

  4. 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.

  5. Stapled endosome disrupting alginate particles for cytosolic delivery of cations.

    PubMed

    Acharya, Abhinav P; Little, Steven R

    2015-01-01

    Divalent cations, the most prevalent minerals in the body, are responsible for a wide variety of cellular functions including signaling, proliferation, differentiation and cell death, and therefore their transmembrane transportation is tightly regulated. Despite the importance of divalent cations in cell activity, there are currently no intracellular delivery methods for divalent cations or modulation of intracellular levels of minerals. Here, we describe endosome disrupting alginate nanoparticles termed Alginoketals, which can deliver divalent cations to the cytosol of the cells. Alginoketals are generated by crosslinking alginic acid with endosome disrupting ketals, and using divalent cations as the stapling or binding agent. We show that Alginoketals were able to deliver copper (II) in the cytosol of the cancer cells thereby disrupting copper homeostasis and inducing cell death via accumulation of hydrogen peroxide. Alginoketal-copper (II)-based particles act as superoxide dismutase mimics and are the first class of divalent cation delivery vehicles, with potential application in cancer therapy, regenerative medicine and drug delivery.

  6. 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.

  7. Influence of interlayer cations on organic intercalation of montmorillonite.

    PubMed

    Wu, Limei; Liao, Libing; Lv, Guocheng

    2015-09-15

    The influence of the types of interlayer cations on organic intercalation of montmorillonite (Mt) was studied in this paper. The distribution of Na(+), K(+), Mg(2+), Ca(2+) and Fe(3+) in montmorillonite interlayer, their interaction with structure layers and the effect of interlayer cations on the basal spacing of Mt, the amount of binding water for different interlayer cations and the binding force between them were investigated systematically. 1-Hexadecy1-3-methylimidazolium chloride monohydrate (C16mimCl) was intercalated into montmorillonites with different interlayer cations. The influence of interlayer cations on organic intercalation was investigated. Molecular dynamics (MD) modeling was used to speculate the interlayer microstructures of the organically intercalated Mt with different interlayer cations. These simulations help to predict the microstructure of organo-Mt and guide their relevant engineering applications. PMID:26001131

  8. 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.

  9. Chapter 17 - Engineering cationic liposome siRNA complexes for in vitro and in vivo delivery.

    PubMed

    Podesta, Jennifer E; Kostarelos, Kostas

    2009-01-01

    RNA interference, the sequence-specific silencing of gene expression by introduction of short interfering RNA (siRNA) is a powerful tool that that the potential to act as a therapeutic agent and the advantage of decreasing toxic effects on normal tissue sometimes seen with conventional treatments i.e. small molecule inhibitors. Naked, unmodified siRNA is poorly taken up by cells and is subject to degradation when exposed to blood proteins during systemic administration. It has also been shown to produce non-specific immune response as well as having the potential to generate 'off-target' effects. Therefore there is a requirement for a delivery system to not only protect the siRNA and facilitate its uptake, but additionally to offer the potential for targeted delivery with an aim of exploiting the high specificity afforded by RNA interference. Cationic liposomes are the most studied, non-viral delivery system used for nucleic acid delivery. As such, the use of cationic liposomes is promising for siRNA for delivery. Furthermore, polyethylene glycol (PEG) can be incorporated into the liposome formulation to create sterically stabilized or 'stealth' liposomes. Addition of PEG can reduce recognition by the reticuloendothelial system (RES) thereby prolonging circulation time. Here we describe a methodology for the complexation of siRNA with cationic liposomes and PEGylated liposomes using two protocols: mixing and encapsulation. Moreover, the different formulations are compared head to head to demonstrate their efficacy for gene silencing.

  10. Facilitating submetering implementation. Final report

    SciTech Connect

    Bowers, M.A.

    1996-05-01

    Residential submetering is the measurement and billing of electric use in individual apartments in master-metered buildings. In master-metered building situations, residents do not bear electricity costs in proportion to consumption levels. As a result, studies have confirmed that residents in master-metered buildings tend to consume more electricity than residents with individual apartment metering, and have established electrical submetering as an effective energy conservation measure. The New York State Energy Research & Development Authority (NYSERDA) has commissioned a project called Facilitating Submetering Implementation to identify and analyze barriers to the implementation of residential electrical submetering in New York and to formulate recommendations that would facilitate the removal of these barriers, streamlining the process. Experienced professionals in the technical, legal, regulatory, analytical, financial, and other aspects of submetering were retained to interview key interested parties and conduct public forums. This and other data were then analyzed to ascertain the barriers to submetering and develop recommendations designed to reduce or eliminate these barriers. The key barriers to submetering implementation were found to be the Public Service Commission (PSC) requirement for a vote of a majority of shareholders (for coops and condos) and the high initial cost that cannot easily be recouped by owners of both rental and shareholder-owned buildings. The key recommendations are to repeal the voting requirement, maintain the utility incentives, adopt a uniform dispute resolution mechanism, and increase awareness through an Ad-hoc Submetering Committee and supporting educational materials. Other funding sources not fully available can also be made available with regulatory agency support.

  11. Diffusion of ion-exchanging electrolytes in montmorillonite gels

    SciTech Connect

    Jahnke, F.M.

    1987-01-01

    The primary contributions of this work are: (1) Development of a unique radially perfused diffusion cell suitable for measuring transient diffusion rates in compacted, highly adsorbing and swelling porous media such as montmorillonite clay gels; (2) examination of the effective diffusion coefficient (D{sub 6}) of electrolytes in montmorillonite clay gels; and (3) Measurement of the transient diffusion rates of cesium, chloride and tritium in 15 w/o montmorillonite clay gels at pH 9 and sodium chloride backgrounds of 10{sup {minus}1} to 10{sup {minus}3} kmol/m{sup 3}. Results are interpreted by using the dilute limit of the multicomponent transport equations derived for species migration in a single clay pore after macroscopic averaging. The tortuosity of the clay gel is found by tritium diffusion. Transient chloride diffusion rates are found to be at molecular rates. Negative adsorption of anions from the clay gel, required for an a priori prediction of chloride profiles, are calculated from site-binding theory. Surface diffusion is the primary mode of cesium transport in montmorillonite clay gels. Migration of cesium is primarily along the inner Helmholtz plane of clay particles. The primary implication for the montmorillonite clay-based packing as a nuclear waste migration barrier is that surface diffusion must be included to describe properly diffusion rates of either anions or cations. Currently surface diffusion is neglected and cesium penetration into the packing is drastically underestimated. Penetration depths of anions is grossly overestimated. In either case, the appropriate diffusion coefficient of ions in compacted packing will be in considerable error relative to current design recommendations.

  12. Solvent-dependent cation exchange in metal-organic frameworks.

    PubMed

    Brozek, Carl K; Bellarosa, Luca; Soejima, Tomohiro; Clark, Talia V; López, Núria; Dincă, Mircea

    2014-06-01

    We investigated which factors govern the critical steps of cation exchange in metal-organic frameworks by studying the effect of various solvents on the insertion of Ni(2+) into MOF-5 and Co(2+) into MFU-4l. After plotting the extent of cation insertion versus different solvent parameters, trends emerge that offer insight into the exchange processes for both systems. This approach establishes a method for understanding critical aspects of cation exchange in different MOFs and other materials.

  13. Multilamellar structures of DNA complexes with cationic liposomes.

    PubMed

    Dan, N

    1997-10-01

    Studies of DNA complexes with cationic liposomes are prompted by the search for nonviral DNA carriers for gene therapy. Recent experiments have identified a stable multilamellar phase in which ordered smectic layers of DNA alternate with cationic bilayers. In this paper we identify the forces governing DNA adsorption on cationic lamellae, including a membrane-induced attraction between the adsorbed DNA. Calculating the DNA interhelical spacing as a function of system composition, the model successfully explains recent surprising observations.

  14. Solvation structure and transport properties of alkali cations in dimethyl sulfoxide under exogenous static electric fields

    SciTech Connect

    Kerisit, Sebastien; Vijayakumar, M. E-mail: karl.mueller@pnnl.gov; Han, Kee Sung; Mueller, Karl T. E-mail: karl.mueller@pnnl.gov

    2015-06-14

    A combination of molecular dynamics simulations and pulsed field gradient nuclear magnetic resonance spectroscopy is used to investigate the role of exogenous electric fields on the solvation structure and dynamics of alkali ions in dimethyl sulfoxide (DMSO) and as a function of temperature. Good agreement was obtained, for select alkali ions in the absence of an electric field, between calculated and experimentally determined diffusion coefficients normalized to that of pure DMSO. Our results indicate that temperatures of up to 400 K and external electric fields of up to 1 V nm{sup −1} have minimal effects on the solvation structure of the smaller alkali cations (Li{sup +} and Na{sup +}) due to their relatively strong ion-solvent interactions, whereas the solvation structures of the larger alkali cations (K{sup +}, Rb{sup +}, and Cs{sup +}) are significantly affected. In addition, although the DMSO exchange dynamics in the first solvation shell differ markedly for the two groups, the drift velocities and mobilities are not significantly affected by the nature of the alkali ion. Overall, although exogenous electric fields induce a drift displacement, their presence does not significantly affect the random diffusive displacement of the alkali ions in DMSO. System temperature is found to have generally a stronger influence on dynamical properties, such as the DMSO exchange dynamics and the ion mobilities, than the presence of electric fields.

  15. Tonoplast Aquaporins Facilitate Lateral Root Emergence.

    PubMed

    Reinhardt, Hagen; Hachez, Charles; Bienert, Manuela Désirée; Beebo, Azeez; Swarup, Kamal; Voß, Ute; Bouhidel, Karim; Frigerio, Lorenzo; Schjoerring, Jan K; Bennett, Malcolm J; Chaumont, Francois

    2016-03-01

    Aquaporins (AQPs) are water channels allowing fast and passive diffusion of water across cell membranes. It was hypothesized that AQPs contribute to cell elongation processes by allowing water influx across the plasma membrane and the tonoplast to maintain adequate turgor pressure. Here, we report that, in Arabidopsis (Arabidopsis thaliana), the highly abundant tonoplast AQP isoforms AtTIP1;1, AtTIP1;2, and AtTIP2;1 facilitate the emergence of new lateral root primordia (LRPs). The number of lateral roots was strongly reduced in the triple tip mutant, whereas the single, double, and triple tip mutants showed no or minor reduction in growth of the main root. This phenotype was due to the retardation of LRP emergence. Live cell imaging revealed that tight spatiotemporal control of TIP abundance in the tonoplast of the different LRP cells is pivotal to mediating this developmental process. While lateral root emergence is correlated to a reduction of AtTIP1;1 and AtTIP1;2 protein levels in LRPs, expression of AtTIP2;1 is specifically needed in a restricted cell population at the base, then later at the flanks, of developing LRPs. Interestingly, the LRP emergence phenotype of the triple tip mutants could be fully rescued by expressing AtTIP2;1 under its native promoter. We conclude that TIP isoforms allow the spatial and temporal fine-tuning of cellular water transport, which is critically required during the highly regulated process of LRP morphogenesis and emergence.

  16. The temperature of formation of carbonate in Martian meteorite ALH84001: constraints from cation diffusion

    SciTech Connect

    Hutcheon, I D; Kent, A; Phinney, D L; Ryerson, F J

    1999-08-13

    An important test of the hypothesis that Martian meteorite ALH84001 contains fossil remnants of an ancient Martian biota is the thermal history of the carbonate rosettes associated with the proposed biomarkers. If carbonates formed at temperatures over {approximately} 110 C (the limit for terrestrial life), it is unlikely that these minerals are associated with a terrestrial-like biota.

  17. Updating applied diffusion models

    SciTech Connect

    Weil, J.C.

    1985-01-01

    Most diffusion models currently used in air-quality applications are substantially out of date with understanding of turbulence and diffusion in the planetary boundary layer. Under a Cooperative Agreement with the Environmental Protection Agency, the American Meteorological Society organized a workshop to help improve the basis of such models, their physics and hopefully their performance. Reviews and recommendations were made on models in three areas: diffusion in the convective boundary layer (CBL), diffusion in the stable boundary layer (SBL), and model uncertainty. Progress has been made in all areas, but it is most significant and ready for application to practical models in the case of the CBL. This has resulted from a clear understanding of the vertical structure and diffusion in the CBL, as demonstrated by laboratory experiments, numerical simulations, and field observations. Understanding of turbulence structure and diffusion in the SBL is less complete and not yet ready for general use in applications.

  18. 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.

  19. Hydroxide Degradation Pathways for Imidazolium Cations. A DFT Study

    SciTech Connect

    Long, H.; Pivovar, B.

    2014-05-15

    Imidazolium cations are promising candidates as covalently tetherable cations for application in anion exchange membranes. They have generated specific interest in alkaline membrane fuel cell applications where ammonium-based cations have been the most commonly applied but have been found to be susceptible to hydroxide attack. In the search for high stability cations, a detailed understanding of the degradation pathways and reaction barriers is required. In this work, we investigate imidazolium and benzimidazolium cations in the presence of hydroxide using density functional theory calculations for their potential in alkaline membrane fuel cells. Moreover, the dominant degradation pathway for these cations is predicted to be the nucleophilic addition–elimination pathway at the C-2 atom position on the imidazolium ring. Steric interferences, introduced by substitutions at the C-2, C-4, and C-5 atom positions, were investigated and found to have a significant, positive impact on calculated degradation energy barriers. Benzimidazolium cations, with their larger conjugated systems, are predicted to degrade much faster than their imidazolium counterparts. Our results provide important insight into designing stable cations for anion exchange membranes. Some of the molecules studied have significantly increased degradation energy barriers suggesting that they could possess significantly improved (several orders of magnitude) durability compared to traditional cations and potentially enable new applications.

  20. Trapping of neutral radicals by aromatic and heterocyclic cation radicals

    SciTech Connect

    Shine, H.J.; Soroka, M.

    1986-09-01

    A considerable amount of knowledge has been accrued during the last 15-20 years on the chemistry of polynuclear aromatic and heterocyclic cation radicals. For the most part, the reactions that have been studied have been of cation radicals with neutral and anionic nucleophiles which lead to addition or substitution products. Classic examples among these reactions are, for example, the reaction of water with the cation radical of 9,10-diphenylanthracene and perylene, and that of water with the thianthrene cation radical. Reactions such as these have been among foundation-establishing studies in the scope and mechanism of cation-radical reactions. Cation radicals can also undergo another type reaction with nucleophies, that is, electron transfer. This possibility leads to two far-reaching and connected questions: can addition and substitution reactions of aromatic cation radicals with nucleophiles be preceded by single electron transfer (SET).; and, can such cation radicals trap neutral radicals. These questions are also then related to another question having even greater impact on organic chemistry: can electrophilic aromatic substitution (ArH + E/sup +/ ..-->.. ArE + H/sup +/) be preceded by SET. The authors have been trying to answer the first two questions about SET and trapping of radicals by combining the two possibilities. That is, they have chosen the reaction of the thianthrene cation radical (represented by the symbol S/sup +./) with grignard reagents, for which two possible routes could be anticipated: either direct addition at sulfur or addition preceded by SET.

  1. Cation trapping by cellular acidic compartments: Beyond the concept of lysosomotropic drugs

    SciTech Connect

    Marceau, François; Bawolak, Marie-Thérèse; Lodge, Robert; Bouthillier, Johanne; Gagné-Henley, Angélique; Gaudreault, René C.; Morissette, Guillaume

    2012-02-15

    “Lysosomotropic” cationic drugs are known to concentrate in acidic cell compartments due to low retro-diffusion of the protonated molecule (ion trapping); they draw water by an osmotic mechanism, leading to a vacuolar response. Several aspects of this phenomenon were recently reexamined. (1) The proton pump vacuolar (V)-ATPase is the driving force of cationic drug uptake and ensuing vacuolization. In quantitative transport experiments, V-ATPase inhibitors, such as bafilomycin A1, greatly reduced the uptake of cationic drugs and released them in preloaded cells. (2) Pigmented or fluorescent amines are effectively present in a concentrated form in the large vacuoles. (3) Consistent with V-ATPase expression in trans-Golgi, lysosomes and endosomes, a fraction of the vacuoles is consistently labeled with trans-Golgi markers and protein secretion and endocytosis are often inhibited in vacuolar cells. (4) Macroautophagic signaling (accumulation of lipidated and membrane-bound LC3 II) and labeling of the large vacuoles by the autophagy effector LC3 were consistently observed in cells, precisely at incubation periods and amine concentrations that cause vacuolization. Vacuoles also exhibit late endosome/lysosome markers, because they may originate from such organelles or because macroautophagosomes fuse with lysosomes. Autophagosome persistence is likely due to the lack of resolution of autophagy, rather than to nutritional deprivation. (5) Increased lipophilicity decreases the threshold concentration for the vacuolar and autophagic cytopathology, because simple diffusion into cells is limiting. (6) A still unexplained mitotic arrest is consistently observed in cells loaded with amines. An extended recognition of relevant clinical situations is proposed for local or systemic drug administration.

  2. Gaseous diffusion system

    DOEpatents

    Garrett, George A.; Shacter, John

    1978-01-01

    1. A gaseous diffusion system comprising a plurality of diffusers connected in cascade to form a series of stages, each of said diffusers having a porous partition dividing it into a high pressure chamber and a low pressure chamber, and means for combining a portion of the enriched gas from a succeeding stage with a portion of the enriched gas from the low pressure chamber of each stage and feeding it into one extremity of the high pressure chamber thereof.

  3. VUV Photo-processing of PAH Cations: Quantitative Study on the Ionization versus Fragmentation Processes

    NASA Astrophysics Data System (ADS)

    Zhen, Junfeng; Rodriguez Castillo, Sarah; Joblin, Christine; Mulas, Giacomo; Sabbah, Hassan; Giuliani, Alexandre; Nahon, Laurent; Martin, Serge; Champeaux, Jean-Philippe; Mayer, Paul M.

    2016-05-01

    Interstellar polycyclic aromatic hydrocarbons (PAHs) are strongly affected by the absorption of vacuum ultraviolet (VUV) photons in the interstellar medium (ISM), yet the branching ratio between ionization and fragmentation is poorly studied. This is crucial for the stability and charge state of PAHs in the ISM in different environments, affecting in turn the chemistry, the energy balance, and the contribution of PAHs to the extinction and emission curves. We studied the interaction of PAH cations with VUV photons in the 7-20 eV range from the synchrotron SOLEIL beamline, DESIRS. We recorded by action spectroscopy the relative intensities of photo-fragmentation and photo-ionization for a set of eight PAH cations ranging in size from 14 to 24 carbon atoms, with different structures. At photon energies below ˜13.6 eV fragmentation dominates for the smaller species, while for larger species ionization is immediately competitive after the second ionization potential (IP). At higher photon energies all species behave similarly; the ionization yield gradually increases, leveling off between 0.8 and 0.9 at ˜18 eV. Among isomers, PAH structure appears to mainly affect the fragmentation cross section but not the ionization cross section. We also measured the second IP for all species and the third IP for two of them; all are in good agreement with theoretical ones, confirming that PAH cations can be further ionized in the diffuse ISM. Determining actual PAH dication abundances in the ISM will require detailed modeling. Our measured photo-ionization yields for several PAH cations provide a necessary ingredient for such models.

  4. VUV photo-processing of PAH cations: quantitative study on the ionization versus fragmentation processes

    PubMed Central

    Zhen, Junfeng; Castillo, Sarah Rodriguez; Joblin, Christine; Mulas, Giacomo; Sabbah, Hassan; Giuliani, Alexandre; Nahon, Laurent; Martin, Serge; Champeaux, Jean-Philippe; Mayer, Paul M.

    2016-01-01

    Interstellar polycyclic aromatic hydrocarbons (PAHs) are strongly affected by the absorption of vacuum ultraviolet (VUV) photons in the interstellar medium (ISM), yet the branching ratio between ionization and fragmentation is poorly studied. This is crucial for the stability and charge state of PAHs in the ISM in different environments, affecting in turn the chemistry, the energy balance, and the contribution of PAHs to the extinction and emission curves. We studied the interaction of PAH cations with VUV photons in the 7 – 20 eV range from the synchrotron SOLEIL beamline, DESIRS. We recorded by action spectroscopy the relative intensities of photo-fragmentation and photo-ionization for a set of eight PAH cations ranging in size from 14 to 24 carbon atoms, with different structures. At photon energies below ~13.6 eV fragmentation dominates for the smaller species, while for larger species ionization is immediately competitive after the second ionization potential (IP). At higher photon energies, all species behave similarly, the ionization yield gradually increases, leveling off between 0.8 and 0.9 at ~18 eV. Among isomers, PAH structure appears to mainly affect the fragmentation cross section, but not the ionization cross section. We also measured the second IP for all species and the third IP for two of them, all are in good agreement with theoretical ones confirming that PAH cations can be further ionized in the diffuse ISM. Determining actual PAH dication abundances in the ISM will require detailed modeling. Our measured photo-ionization yields for several PAH cations provide a necessary ingredient for such models. PMID:27212712

  5. Increased yields of radical cations by arene addition to irradiated 1,2-dichloroethane

    NASA Astrophysics Data System (ADS)

    Funston, Alison M.; Miller, John R.

    2005-04-01

    Pulse radiolysis in chlorinated hydrocarbon liquids such as 1,2-dichloroethane is a versatile and effective method for the generation of solute radical cations. The addition of a large concentration of toluene or benzene to solutions of 1,2-dichloroethane is found to increase the yield of solute radical cations ( G=0.68 molecules 100 eV -1 in 1,2-dichloroethane (J. Phys. Chem. 83(15) (1979) 1944) by a factor of 2.5. The increased yield is found for solutes which have a potential of ˜1.1 V (vs. SCE) or below for the S + rad /S couple and is due to reaction of the chlorine atom:toluene (π-Cl rad ) complex with the solute. A similar species forms with benzene. π-Cl rad is formed with a yield of G=3.0, and arises principally as a result of geminate recombination of ions. It has an absorption in the visible with λ max 460 nm, ɛ max=1800 M -1 cm -1 and decays with an observed first-order rate constant k=1.12×10 6 s -1. The rate of reaction of the π-Cl • with added solutes ranges from 2.5 to 5×10 9 M -1 s -1. The other oxidant present in the 1,2-dichloroethane/toluene solutions is identified as the toluene cation dimer. This is formed from the 1,2-dichloroethane radical cation with bimolecular rate constant k=1.35×10 10 M -1 s -1 with a radiation chemical yield G=0.5. The rate of reaction of this species with the added solutes is diffusion controlled, k=1-2×10 10 M -1 s -1.

  6. Extended delivery of an anionic drug by contact lens loaded with a cationic surfactant.

    PubMed

    Bengani, Lokendrakumar C; Chauhan, Anuj

    2013-04-01

    Drug eluding contact lenses can be very effective vehicles for ophthalmic drug delivery, but are incapable of releasing drug for more than a few hours. We propose to optimize the interactions of the polymer matrix of the contact lens with the hydrophobic tails of ionic surfactants to adsorb the surfactant molecules on the polymer with high packing and thus create a high surface charge. Ionic drugs can then adsorb on the charged surfactant coated surfaces with high affinity to reduce the transport rates, leading to extended release. Specifically, we show control release of an anionic drug dexamethasone 21-disodium phosphate from poly-hydroxyethyl methacrylate (p-HEMA) contact lenses by utilizing cationic surfactant (cetalkonium chloride). The partition coefficient of the drug increase exponentially with surfactant loading in the gel in at least qualitative agreement with the Debye-Hückel theory. The drug adsorbs on the surfactant covered polymer, and can also diffuse along the surface with diffusivity lower than that for the free drug, leading to a reduction in the effective diffusivity, which is the weighted combination of the free and surface diffusivities. The addition of surfactant did not impact transparency of lenses, and had additional benefits of increase in wettability and significant reduction in protein absorption. With a surfactant loading of about 10%, the drug release duration was increased from about 2 h to 50 h in 1-day ACUVUE(®) contact lenses, proving the viability of using surfactant for increasing drug release durations.

  7. Inpainting using airy diffusion

    NASA Astrophysics Data System (ADS)

    Lorduy Hernandez, Sara

    2015-09-01

    One inpainting procedure based on Airy diffusion is proposed, implemented via Maple and applied to some digital images. Airy diffusion is a partial differential equation with spatial derivatives of third order in contrast with the usual diffusion with spatial derivatives of second order. Airy diffusion generates the Airy semigroup in terms of the Airy functions which can be rewritten in terms of Bessel functions. The Airy diffusion can be used to smooth an image with the corresponding noise elimination via convolution. Also the Airy diffusion can be used to erase objects from an image. We build an algorithm using the Maple package ImageTools and such algorithm is tested using some images. Our results using Airy diffusion are compared with the similar results using standard diffusion. We observe that Airy diffusion generates powerful filters for image processing which could be incorporated in the usual packages for image processing such as ImageJ and Photoshop. Also is interesting to consider the possibility to incorporate the Airy filters as applications for smartphones and smart-glasses.

  8. Multicomponent diffusion revisited

    NASA Astrophysics Data System (ADS)

    Lam, S. H.

    2006-07-01

    The derivation of the multicomponent diffusion law is revisited. Following Furry [Am. J. Phys. 16, 63 (1948)], Williams [Am. J. Phys. 26, 467 (1958); Combustion Theory, 2nd ed. (Benjamin/Cummings , Menlo Park, CA,1985)] heuristically rederived the classical kinetic theory results using macroscopic equations, and pointed out that the dynamics of the mixture fluid had been assumed inviscid. This paper generalizes the derivation, shows that the inviscid assumption can easily be relaxed to add a new term to the classical diffusion law, and the thermal diffusion term can also be easily recovered. The nonuniqueness of the multicomponent diffusion coefficient matrix is emphasized and discussed.

  9. Evaluation of the Facilitated Communication Pilot

    ERIC Educational Resources Information Center

    Cooper-Martin, Elizabeth

    2014-01-01

    The Office of Special Education and Student Services asked the Office of Shared Accountability to evaluate the "Facilitated Communication Pilot." In facilitated communication (FC), people with communication impairments express themselves by typing with the aid of a communication partner, called a facilitator, who provides physical (and…

  10. An experimental analysis of facilitated communication.

    PubMed Central

    Montee, B B; Miltenberger, R G; Wittrock, D; Watkins, N; Rheinberger, A; Stackhaus, J

    1995-01-01

    We evaluated the authorship of messages produced through facilitated communication by 7 adults with moderate or severe mental retardation and their facilitators. The clients had been reported to be communicating fluently through facilitated communication. We controlled the facilitators' access to information to be communicated in two evaluation formats, naming pictures and describing activities. In both formats we conducted three conditions: (a) the facilitator and client had access to the same information, (b) the facilitator did not have access to the picture or activity, and (c) the facilitator was given false information about the picture or activity. The results showed that the clients typed the correct answer only when the facilitator had access to the same information, never typed the correct answer when the facilitator had no information or false information, and typed the picture or activity presented to the facilitator when it was different from the one experienced by the client. These results provide unequivocal evidence for facilitator control of typing during facilitated communication. PMID:7601804

  11. The Teacher and Town Planner as Facilitator.

    ERIC Educational Resources Information Center

    Peel, Deborah

    2000-01-01

    Discussion of theories of facilitation in teaching focuses on citizen participation and the role of the facilitator in town planning. Highlights include hierarchies of learning; student-centered learning; facilitating community participation; information technology skills and interpersonal skills; and a rationale for participation. (LRW)

  12. Technologies and Techniques for Supporting Facilitated Video

    ERIC Educational Resources Information Center

    Linnell, Natalie

    2011-01-01

    Worldwide, demand for education of all kinds is increasing beyond the capacity to provide it. One approach that shows potential for addressing this demand is facilitated video. In facilitated video, an educator is recorded teaching, and that video is sent to a remote site where it is shown to students by a facilitator who creates interaction…

  13. Simultaneous ion-exclusion/cation-exchange chromatography of anions and cations in acid rain waters on a weakly acidic cation-exchange resin by elution with sulfosalicylic acid.

    PubMed

    Tanaka, K; Ohta, K; Haddad, P R; Fritz, J S; Miyanaga, D A; Hu, W; Hasebe, K

    2000-07-01

    A simple, selective, and sensitive method for the simultaneous determination of anions (sulfate, nitrate, and chloride) and cations (sodium, ammonium, potassium, magnesium, and calcium) in acid rain waters was developed using ion-exclusion/ cation-exchange chromatography with conductimetric detection. A weakly acidic cation-exchange resin column (Tosho TSKgel OA-PAK-A) and a sulfosalicylic acid-methanol-water eluent was used. With a mobile phase comprising 1.25 mM sulfosalicylic acid in methanol-water (7.5:92.5) at 1.2 ml/min, simultaneous separation and detection of the above anions and cations was achieved in about 30 min. Linear calibration plots of peak area versus concentration were obtained over the concentration ranges 0-1.0 mM for anions (R=0.9991) and 0-0.5 mM for cations (R=0.9994). Detection limits calculated at S/N=3 ranged from 4.2 to 14.8 ppb for the anions and from 2.4 to 12.1 ppb for the cations. The reproducibility of retention times was 0.14-0.15% relative standard deviation (RSD) for anions and 0.18-0.31% for cations, and reproducibility of chromatographic peak areas was 1.22-1.75% RSD for anions and 1.81-2.10% for cations. The method was applied successfully to the simultaneous determination of anions and cations in aerosols transported from mainland China to central Japan, as determined by a meteorological satellite data analyzer.

  14. Experimental study of vortex diffusers

    SciTech Connect

    Shakerin, S.; Miller, P.L.

    1995-11-01

    This report documents experimental research performed on vortex diffusers used in ventilation and air-conditioning systems. The main objectives of the research were (1) to study the flow characteristics of isothermal jets issuing from vortex diffusers, (2) to compare the vortex diffuser`s performance with that of a conventional diffuser, and (3) to prepare a report that disseminates the results to the designers of ventilation and air-conditioning systems. The researchers considered three diffusers: a conventional round ceiling diffuser and two different styles of vortex diffusers. Overall, the vortex diffusers create slightly more induction of ambient air in comparison to the conventional diffuser.

  15. The structures of cyclic dihydronium cations.

    PubMed

    Wallace, Sonjae; Huang, Lulu; Massa, Lou; Mukhopadhyay, Uday; Bernal, Ivan; Karle, Jerome

    2007-10-23

    Recent experimental discoveries have revealed the existence of hitherto unexpected cyclic hydronium di-cations trapped within crystal structures. The molecular formulas are (H(14)O(6))(2+), present as two isomers, four- and six-member cyclic structures, and (H(18)O(8))(2+), an eight-member cyclic structure. As these unprecedented hydronium species are stabilized by the crystal structures in which they are captured, the question arises whether they could be stable as independent species as, for example, in solution or gas phase. Quantum mechanical density functional theory calculations are used to investigate this question. We find these doubly charged cyclic hydronium structures to be energetically stable and, as between the four- and six-member structures, the former has more binding energy than the latter. We also determine the theoretically optimized structures for all three ions and give their calculated atomic charges for both their crystal and optimized geometries.

  16. Retention of Cationic Starch onto Cellulose Fibres

    NASA Astrophysics Data System (ADS)

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

    2008-08-01

    Three methods of cationic starch titration were used to quantify its retention on cellulose fibres, namely: (i) the complexation of CS with iodine and measurement of the absorbency of the ensuing blue solution by UV-vis spectroscopy; (ii) hydrolysis of the starch macromolecules followed by the conversion of the resulting sugars to furan-based molecules and quantifying the ensuing mixture by measuring their absorbance at a Ι of 490 nm, using the same technique as previous one and; finally (iii) hydrolysis of starch macromolecules by trifluoro-acetic acid and quantification of the sugars in the resulting hydrolysates by high performance liquid chromatography. The three methods were found to give similar results within the range of CS addition from 0 to 50 mg per g of cellulose fibres.

  17. Capturing dynamic cation hopping in cubic pyrochlores

    NASA Astrophysics Data System (ADS)

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

    2011-08-01

    In direct contrast to recent reports, density functional theory predicts that the most stable structure of Bi2Ti2O7 pyrochlore is a cubic Fd3¯m space group by accounting for atomic displacements. The displaced Bi occupies the 96g(x,x,z) Wyckoff position with six equivalent sites, which create multiple local minima. Using nudged elastic band method, the transition states of Bi cation hopping between equivalent minima were investigated and an energy barrier between 0.11 and 0.21 eV was determined. Energy barriers associated with the motion of Bi between equivalent sites within the 96g Wyckoff position suggest the presence of dielectric relaxation in Bi2Ti2O7.

  18. Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface.

    PubMed

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

    2016-09-01

    Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO3) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H2O and CO2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, ) by the positively charged oxygen vacancies () enriched at the surface. Here we show that reducing the surface concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O2 molecules. We take La0.8Sr0.2CoO3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a 'volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss. PMID:27295099

  19. Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  20. 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.

  1. 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

  2. Cation Intermixing And Electronic Deviations At The Insulating LaCrO3/SrTiO3(001) Interface

    SciTech Connect

    Colby, Robert J.; Qiao, Liang; Zhang, Hongliang; Shutthanandan, V.; Ciston, Jim; Kabius, Bernd C.; Chambers, Scott A.

    2013-10-29

    The interface between polar perovskite LaCrO3 (LCO) and non-polar SrTiO3(001) (STO), grown by molecular beam epitaxy, is examined using a combination of electron microscopy, spectroscopy, and Rutherford backscattering spectrometry. The LCO/STO(001) interface is insulating, a potential counter example for the claim that polar/nonpolar perovskite interfaces should be conductive by virtue of an electronic reconstruction to alleviate the polar discontinuity. The A-site cations of these ABO3 perovskites are found to diffuse across the interface to a greater extent than the B-site cations, based on high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), energy dispersive x-ray spectroscopy (EDS) and electron energy loss spectroscopy (EELS). The B-site cation valences are shown to be partially reduced near the interface by analysis of EELS near-edge structures. The location and direction of these electronic modifications do not intuitively compensate the charge imbalance imposed by uneven cation inter-diffusion, and yet both the film and interface are insulating. These results highlight the importance of both the physical and electronic structure of such complex interfaces in determining their characteristics. Furthermore, the extent of inter-diffusion is shown to increase with increasing LCO film thickness, suggesting a potential mechanism behind the critical thickness for interfacial conductivity in other polar/non-polar oxide systems, and a fundamental limitation on the formation of abrupt interfaces in LCO/STO(001).

  3. Coupled chemical and diffusion model for compacted bentonite

    SciTech Connect

    Olin, M.; Lehikoinen, J.; Muurinen, A.

    1995-12-31

    A chemical equilibrium model has been developed for ion-exchange and to a limited extent for other reactions, such as precipitation or dissolution of calcite or gypsum, in compacted bentonite water systems. The model was successfully applied to some bentonite experiments, especially as far as monovalent ions were concerned. The fitted log-binding constants for the exchange of sodium for potassium, magnesium, and calcium were 0.27, 1.50, and 2.10, respectively. In addition, a coupled chemical and diffusion model has been developed to take account of diffusion in pore water, surface diffusion and ion-exchange.d the model was applied to the same experiments as the chemical equilibrium model, and its validation was found partly successful. The above values for binding constants were used also in the coupled model. The apparent (both for anions and cations) and surface diffusion (only for cations) constants yielding the best agreement between calculated and experimental data were 3.0 {times} 10{sup {minus}11} m{sup 2}/s and 6.0 {times} 10{sup {minus}12} m{sup 2}/s, respectively. These values are questionable, however, as experimental results good enough for fitting are currently not available.

  4. Some Conditions that Facilitate Progress Toward the Utilization of New Products or Practices in Local Schools.

    ERIC Educational Resources Information Center

    Papagiannis, Meredith; Richardson, Gerry

    This study examines the relative importance that local school personnel ascribe to certain facilitating conditions identified in the diffusion literature: administrative support of the change process, faculty motivation toward school improvement efforts, participatory decision-making, inservice training efforts, internal advocacy groups, linkage…

  5. Crystal structure of channelrhodopsin, a light-gated cation channel - all cations lead through the monomer.

    PubMed

    Kato, Hideaki E; Nureki, Osamu

    2013-01-01

    Channelrhodopsin (ChR) is a light-gated cation channel derived from green algae. Since the inward flow of cations triggers the neuron firing, neurons expressing ChRs can be optically controlled even within freely moving mammals. Although ChR has been broadly applied to neuro-science research, little is known about its molecular mechanisms. We determined the crystal structure of chimeric ChR at 2.3 Å resolution and revealed its molecular architecture. The integration of structural, electrophysio-logical, and computational analyses provided insight into the molecular basis for the channel function of ChR, and paved the way for the principled design of ChR variants with novel properties. PMID:27493541

  6. Theoretical study of the electronically excited radical cations of naphthalene and anthracene as archetypal models for astrophysical observations. Part II. Dynamics consequences.

    PubMed

    Ghanta, S; Reddy, V Sivaranjana; Mahapatra, S

    2011-08-28

    Nuclear dynamics is investigated theoretically from first principles by employing the ab initio vibronic models of the prototypical naphthalene and anthracene radical cations developed in Part I. This Part is primarily aimed at corroborating a large amount of available experimental data with a specific final goal to establish an unambiguous link with the current observations in astrophysics and astronomy. The detailed analyses presented here perhaps establish that these two prototypical polycyclic aromatic hydrocarbon radical cations are indeed potential carriers of the observed diffuse interstellar bands. PMID:21750791

  7. Cosmology with matter diffusion

    SciTech Connect

    Calogero, Simone; Velten, Hermano E-mail: velten@cce.ufes.br

    2013-11-01

    We construct a viable cosmological model based on velocity diffusion of matter particles. In order to ensure the conservation of the total energy-momentum tensor in the presence of diffusion, we include a cosmological scalar field φ which we identify with the dark energy component of the universe. The model is characterized by only one new degree of freedom, the diffusion parameter σ. The standard ΛCDM model can be recovered by setting σ = 0. If diffusion takes place (σ > 0) the dynamics of the matter and of the dark energy fields are coupled. We argue that the existence of a diffusion mechanism in the universe may serve as a theoretical motivation for interacting models. We constrain the background dynamics of the diffusion model with Supernovae, H(z) and BAO data. We also perform a perturbative analysis of this model in order to understand structure formation in the universe. We calculate the impact of diffusion both on the CMB spectrum, with particular attention to the integrated Sachs-Wolfe signal, and on the matter power spectrum P(k). The latter analysis places strong constraints on the magnitude of the diffusion mechanism but does not rule out the model.

  8. Speckle reducing anisotropic diffusion.

    PubMed

    Yu, Yongjian; Acton, Scott T

    2002-01-01

    This paper provides the derivation of speckle reducing anisotropic diffusion (SRAD), a diffusion method tailored to ultrasonic and radar imaging applications. SRAD is the edge-sensitive diffusion for speckled images, in the same way that conventional anisotropic diffusion is the edge-sensitive diffusion for images corrupted with additive noise. We first show that the Lee and Frost filters can be cast as partial differential equations, and then we derive SRAD by allowing edge-sensitive anisotropic diffusion within this context. Just as the Lee and Frost filters utilize the coefficient of variation in adaptive filtering, SRAD exploits the instantaneous coefficient of variation, which is shown to be a function of the local gradient magnitude and Laplacian operators. We validate the new algorithm using both synthetic and real linear scan ultrasonic imagery of the carotid artery. We also demonstrate the algorithm performance with real SAR data. The performance measures obtained by means of computer simulation of carotid artery images are compared with three existing speckle reduction schemes. In the presence of speckle noise, speckle reducing anisotropic diffusion excels over the traditional speckle removal filters and over the conventional anisotropic diffusion method in terms of mean preservation, variance reduction, and edge localization.

  9. Galactic Diffuse Emissions

    SciTech Connect

    Digel, Seth W.; /SLAC

    2007-10-25

    Interactions of cosmic rays with interstellar nucleons and photons make the Milky Way a bright, diffuse source of high-energy {gamma}-rays. Observationally, the results from EGRET, COMPTEL, and OSSE have now been extended to higher energies by ground-based experiments, with detections of diffuse emission in the Galactic center reported by H.E.S.S. in the range above 100 GeV and of diffuse emission in Cygnus by MILAGRO in the TeV range. In the range above 100 keV, INTEGRAL SPI has found that diffuse emission remains after point sources are accounted for. I will summarize current knowledge of diffuse {gamma}-ray emission from the Milky Way and review some open issues related to the diffuse emission -- some old, like the distribution of cosmic-ray sources and the origin of the 'excess' of GeV emission observed by EGRET, and some recently recognized, like the amount and distribution of molecular hydrogen not traced by CO emission -- and anticipate some of the advances that will be possible with the Large Area Telescope on GLAST. We plan to develop an accurate physical model for the diffuse emission, which will be useful for detecting and accurately characterizing emission from Galactic point sources as well as any Galactic diffuse emission from exotic processes, and for studying the unresolved extragalactic emission.

  10. Investigating Diffusion with Technology

    ERIC Educational Resources Information Center

    Miller, Jon S.; Windelborn, Augden F.

    2013-01-01

    The activities described here allow students to explore the concept of diffusion with the use of common equipment such as computers, webcams and analysis software. The procedure includes taking a series of digital pictures of a container of water with a webcam as a dye slowly diffuses. At known time points, measurements of the pixel densities…

  11. Anatomy of Particle Diffusion

    ERIC Educational Resources Information Center

    Bringuier, E.

    2009-01-01

    The paper analyses particle diffusion from a thermodynamic standpoint. The main goal of the paper is to highlight the conceptual connection between particle diffusion, which belongs to non-equilibrium statistical physics, and mechanics, which deals with particle motion, at the level of third-year university courses. We start out from the fact…

  12. The preparation of calcium carbonate crystals regulated by mixed cationic/cationic surfactants

    NASA Astrophysics Data System (ADS)

    Zhao, Yingyuan; Li, Shuxia; Yu, Li; Liu, Yonghui; Wang, Xiaoqing; Jiao, Jingjing

    2011-06-01

    Cationic surfactants, didodecyldimethylammonium bromide (DDAB), 1-dodecyl-3-methylimidazolium bromide ([C 12mim]Br) and DDAB/[C 12mim]Br mixture were used to induce the formation of calcium carbonate (CaCO 3) crystals at ambient temperature. The obtained CaCO 3 particles were characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD) and thermogravimetric analysis (TGA). The morphologies of CaCO 3 crystals changed from laminated cube to sphericity and string shape with the increase of DDAB and [C 12mim]Br concentration, respectively. Flower-shaped CaCO 3 crystals were synthesized in the mixed DDAB/[C 12mim]Br system. More importantly, it was found that the complete conversion from calcite to vaterite was achieved at room temperature only through changing DDAB concentration. The regulations of DDAB and [C 12mim]Br to CaCO 3 crystals have been compared with that of dodecyltrimethylammonium bromide (DTAB) in our previous work and possible mechanisms have been proposed. It is shown that the cationic surfactants can control the crystallization of CaCO 3 and the number of hydrophobic alkyl chains of cationic surfactants might be more effective in modulating the crystallization of vaterite than the head groups.

  13. 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.

  14. Hypergolic ionic liquids with the 2,2-dialkyltriazanium cation.

    PubMed

    Gao, Haixiang; Joo, Young-Hyuk; Twamley, Brendan; Zhou, Zhiqiang; Shreeve, Jean'ne M

    2009-01-01

    No flame, no gain: A hypergolic mixture is composed of stable species that readily react/ignite on molecular contact. Both the anion and the cation in an ionic liquid play prominent roles in determining hypergolic properties as well as ignition delay times. With the 2,2-dialkyltriazanium cation, salts with nitrate, chloride, nitrocyanamide, and dicyanamide anions are hypergolic. PMID:19266508

  15. 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...

  16. 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...

  17. 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.

  18. 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.

  19. Combustor diffuser interaction program

    NASA Technical Reports Server (NTRS)

    Srinivasan, Ram; Thorp, Daniel

    1986-01-01

    Advances in gas turbine engine performance are achieved by using compressor systems with high stage loading and low part count, which result in high exit Mach numbers. The diffuser and combustor systems in such engines should be optimized to reduce system pressure loss and to maximize the engine thrust-to-weight ratio and minimize length. The state-of-the-art combustor-diffuser systems do not meet these requirements. Detailed understanding of the combustor-diffuser flow field interaction is required for designing advanced gas turbine engines. An experimental study of the combustor-diffuser interaction (CDI) is being conducted to obtain data for the evaluation and improvement of analytical models applicable to a wide variety of diffuser designs. The CDI program consists of four technical phases: Literature Search; Baseline Configuration; Parametric Configurations; and Performance Configurations. Phase 2 of the program is in progress.

  20. Diffusion in Coulomb crystals.

    PubMed

    Hughto, J; Schneider, A S; Horowitz, C J; Berry, D K

    2011-07-01

    Diffusion in Coulomb crystals can be important for the structure of neutron star crusts. We determine diffusion constants D from molecular dynamics simulations. We find that D for Coulomb crystals with relatively soft-core 1/r interactions may be larger than D for Lennard-Jones or other solids with harder-core interactions. Diffusion, for simulations of nearly perfect body-centered-cubic lattices, involves the exchange of ions in ringlike configurations. Here ions "hop" in unison without the formation of long lived vacancies. Diffusion, for imperfect crystals, involves the motion of defects. Finally, we find that diffusion, for an amorphous system rapidly quenched from Coulomb parameter Γ=175 to Coulomb parameters up to Γ=1750, is fast enough that the system starts to crystalize during long simulation runs. These results strongly suggest that Coulomb solids in cold white dwarf stars, and the crust of neutron stars, will be crystalline and not amorphous. PMID:21867316

  1. Diffusion in Coulomb crystals.

    PubMed

    Hughto, J; Schneider, A S; Horowitz, C J; Berry, D K

    2011-07-01

    Diffusion in Coulomb crystals can be important for the structure of neutron star crusts. We determine diffusion constants D from molecular dynamics simulations. We find that D for Coulomb crystals with relatively soft-core 1/r interactions may be larger than D for Lennard-Jones or other solids with harder-core interactions. Diffusion, for simulations of nearly perfect body-centered-cubic lattices, involves the exchange of ions in ringlike configurations. Here ions "hop" in unison without the formation of long lived vacancies. Diffusion, for imperfect crystals, involves the motion of defects. Finally, we find that diffusion, for an amorphous system rapidly quenched from Coulomb parameter Γ=175 to Coulomb parameters up to Γ=1750, is fast enough that the system starts to crystalize during long simulation runs. These results strongly suggest that Coulomb solids in cold white dwarf stars, and the crust of neutron stars, will be crystalline and not amorphous.

  2. Optimal multi-community network modularity for information diffusion

    NASA Astrophysics Data System (ADS)

    Wu, Jiaocan; Du, Ruping; Zheng, Yingying; Liu, Dong

    2016-02-01

    Studies demonstrate that community structure plays an important role in information spreading recently. In this paper, we investigate the impact of multi-community structure on information diffusion with linear threshold model. We utilize extended GN network that contains four communities and analyze dynamic behaviors of information that spreads on it. And we discover the optimal multi-community network modularity for information diffusion based on the social reinforcement. Results show that, within the appropriate range, multi-community structure will facilitate information diffusion instead of hindering it, which accords with the results derived from two-community network.

  3. Solid Solutions of Rare Earth Cations in Mesoporous Anatase Beads and Their Performances in Dye-Sensitized Solar Cells

    PubMed Central

    Cavallo, Carmen; Salleo, Alberto; Gozzi, Daniele; Di Pascasio, Francesco; Quaranta, Simone; Panetta, Riccardo; Latini, Alessandro

    2015-01-01

    Solid solutions of the rare earth (RE) cations Pr3+, Nd3+, Sm3+, Gd3+, Er3+ and Yb3+ in anatase TiO2 have been synthesized as mesoporous beads in the concentration range 0.1–0.3% of metal atoms. The solid solutions were have been characterized by XRD, SEM, diffuse reflectance UV-Vis spectroscopy, BET and BJH surface analysis. All the solid solutions possess high specific surface areas, up to more than 100 m2/g. The amount of adsorbed dye in each photoanode has been determined spectrophotometrically. All the samples were tested as photoanodes in dye-sensitized solar cells (DSSCs) using N719 as dye and a nonvolatile, benzonitrile based electrolyte. All the cells were have been tested by conversion efficiency (J–V), quantum efficiency (IPCE), electrochemical impedance spectroscopy (EIS) and dark current measurements. While lighter RE cations (Pr3+, Nd3+) limit the performance of DSSCs compared to pure anatase mesoporous beads, cations from Sm3+ onwards enhance the performance of the devices. A maximum conversion efficiency of 8.7% for Er3+ at a concentration of 0.2% has been achieved. This is a remarkable efficiency value for a DSSC employing N719 dye without co-adsorbents and a nonvolatile electrolyte. For each RE cation the maximum performances are obtained for a concentration of 0.2% metal atoms. PMID:26577287

  4. A membrane-free cation selective water-gated transistor.

    PubMed

    Althagafi, Talal M; Al Baroot, Abbad F; Algarni, Saud A; Grell, Martin

    2016-10-01

    Sensors for the detection of waterborne cations are of great practical interest, and chemistry has synthesised a formidable catalogue of cation selective complexation agents ('ionophores') as selective sensitisers. Current ionophore-based sensors separate the complexation of the cation by the ionophore, and the transduction of complexation into an electrical signal, into separate components. We here unite both functions into a single, sensitised semiconducting layer of a water-gated organic thin film transistor (OTFT). The resulting OTFT transduces waterborne cations into an electrical signal with same selectivity, sensitivity, and limit of detection as established sensors at much simplified preparation and operation. This opens a new route to apply the 'ionophore' family of functional organic materials in practical cation sensors.

  5. A membrane-free cation selective water-gated transistor.

    PubMed

    Althagafi, Talal M; Al Baroot, Abbad F; Algarni, Saud A; Grell, Martin

    2016-10-01

    Sensors for the detection of waterborne cations are of great practical interest, and chemistry has synthesised a formidable catalogue of cation selective complexation agents ('ionophores') as selective sensitisers. Current ionophore-based sensors separate the complexation of the cation by the ionophore, and the transduction of complexation into an electrical signal, into separate components. We here unite both functions into a single, sensitised semiconducting layer of a water-gated organic thin film transistor (OTFT). The resulting OTFT transduces waterborne cations into an electrical signal with same selectivity, sensitivity, and limit of detection as established sensors at much simplified preparation and operation. This opens a new route to apply the 'ionophore' family of functional organic materials in practical cation sensors. PMID:27433556

  6. EXP-1 is an excitatory GABA-gated cation channel.

    PubMed

    Beg, Asim A; Jorgensen, Erik M

    2003-11-01

    Gamma-aminobutyric acid (GABA) mediates fast inhibitory neurotransmission by activating anion-selective ligand-gated ion channels. Although electrophysiological studies indicate that GABA may activate cation-selective ligand-gated ion channels in some cell types, such a channel has never been characterized at the molecular level. Here we show that GABA mediates enteric muscle contraction in the nematode Caenorhabditis elegans via the EXP-1 receptor, a cation-selective ligand-gated ion channel. The EXP-1 protein resembles ionotropic GABA receptor subunits in almost all domains. In the pore-forming domain of EXP-1, however, the residues that confer anion selectivity are exchanged for those that specify cation selectivity. When expressed in Xenopus laevis oocytes, EXP-1 forms a GABA receptor that is permeable to cations and not anions. We conclude that some of the excitatory functions assigned to GABA are mediated by cation channels rather than by anion channels.

  7. High-performance ion-exclusion/cation-exchange chromatography of anions and cations in acid rain waters on a weakly acidic cation-exchange resin.

    PubMed

    Tanaka, K; Ohta, K; Haddad, P R; Fritz, J S; Miyanaga, A; Hu, W; Hasebe, K; Lee, K P; Sarzanini, C

    2001-06-22

    A new method for the simultaneous determination of anions (sulfate, nitrate, and chloride) and cations (sodium, ammonium, potassium, magnesium, and calcium) in acid rain waters was investigated using high-performance ion-exclusion/cation-exchange chromatography with conductimetric detection on a separation column packed with a polymethacrylate-based weakly acidic cation-exchange resin in the hydrogen-form and an eluent comprising 1.5 mM sulfosalicylic acid-6 mM 18-crown-6 at pH 2.6, operated at 1.5 ml/min. Effective separation and highly sensitive conductimetric detection for the anions and the cations was achieved in about 14 min. Since the ionic balance (equivalents of anions/equivalents of cations) of acid rain waters of different pH (4.40-4.67) ranged from 0.97 to 0.94, evaluation of the water quality of acid rain was possible. This method was successfully applied to the simultaneous determination of the anions and the cations in acid rain transported from mainland China and North Korea to central Japan monitored by a meteorological satellite data analyzer.

  8. Helium Diffusion in Olivine

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

    Diffusion of helium has been characterized in natural Fe-bearing olivine (~Fo90) and synthetic forsterite. Polished, oriented slabs of olivine were implanted with 3He, at 100 keV at a dose of 5x1015/cm2 or at 3.0 MeV at a dose of 1x1016/cm2. A set of experiments on the implanted olivine were run in 1-atm furnaces. In addition to the one-atm experiments, experiments on implanted samples were also run at higher pressures (2.6 and 2.7 GPa) to assess the potential effects of pressure on He diffusion and the applicability of the measured diffusivities in describing He transport in the mantle. The high-pressure experiments were conducted in a piston-cylinder apparatus using an "ultra-soft" pressure cell, with the diffusion sample directly surrounded by AgCl. 3He distributions following experiments were measured with Nuclear Reaction Analysis using the reaction 3He(d,p)4He. This direct profiling method permits us to evaluate anisotropy of diffusion, which cannot be easily assessed using bulk-release methods. For diffusion in forsterite parallel to c we obtain the following Arrhenius relation over the temperatures 250-950°C: D = 3.91x10-6exp(-159 ± 4 kJ mol-1/RT) m2/sec. The data define a single Arrhenius line spanning more than 7 orders of magnitude in D and 700°C in temperature. Diffusion parallel to a appears slightly slower, yielding an activation energy for diffusion of 135 kJ/mol and a pre-exponential factor of 3.73x10-8 m2/sec. Diffusion parallel to b is slower than diffusion parallel to a (by about two-thirds of a log unit); for this orientation an activation energy of 138 kJ/mol and a pre-exponential factor of 1.34x10-8 m2/sec are obtained. This anisotropy is broadly consistent with observations for diffusion of Ni and Fe-Mg in olivine. Diffusion in Fe-bearing olivine (transport parallel to b) agrees within uncertainty with findings for He diffusion in forsterite. The higher-pressure experiments yield diffusivities in agreement with those from the 1-atm

  9. An experimental assessment of facilitated communication.

    PubMed

    Wheeler, D L; Jacobson, J W; Paglieri, R A; Schwartz, A A

    1993-02-01

    This report presents a quantitative study of facilitated communication. Participants were 12 people living at an institutional autism program and 9 people who provided them with facilitated communication support. These subjects were the 12 most competent producers of facilitated communication in the program. They were shown pictures of familiar objects and asked to type the names of the objects under three conditions: (a) assisted typing with facilitators unaware of the content of the stimulus picture, (b) unassisted typing, and (c) a condition in which the participants and facilitators were each shown pictures at the same time. In this last condition the paired pictures were either the same or different, and the participant's typing was facilitated to label or describe the picture. These participants were unable to succeed in the tasks without facilitator assistance. On trials when the facilitators and participants had different pictures, the only "correct" labels were for pictures shown to the facilitators and not shown to the participants. This finding demonstrates that the facilitators were unknowingly determining what was typed.

  10. Hierarchical modelling of solute diffusion in clays: From the molecular to the continuum scale

    NASA Astrophysics Data System (ADS)

    Gimmi, T.; Churakov, S.

    2009-04-01

    The diffusion properties of clays are most often investigated in laboratory small-scale experiments using uncharged, anionic, and cationic tracers. Typically, the flux of anions through clay samples is lower than that of water tracers like tritiated water. This is explained by anion exclusion effects, which push back anions from the charged clay surfaces towards the centre of the pores and thus reduce the anion accessible porosity to half or less of the water accessible porosity. The diffusion of cations is slowed down because of sorption to the negatively charged clay surfaces. In certain cases, however, the cation flux is larger than expected from the sorption capacity, which is often attributed to surface diffusion, that is, a diffusion of sorbed cations along the clay interlayers or along external surfaces. The consistent description of such phenomena like anion exclusion and surface diffusion with continuum-scale models is rather complicated and relies mostly on empirical parameters. A consistent prediction requires consideration of pore-scale processes, because the ion or tracer specific diffusion behaviour depends on the type and the precise arrangement of the clay phases within the sample. In this presentation, we report on our approach to upscale the specific transport behaviour of anions, cations, and water tracers from the molecular or pore scale to the continuum scale. We developed a random walk model that operates on a pore-scale description of the clay structure. Obtaining such a description for clays is itself a difficult task, because it is hardly possible to directly visualise the very small pores in the nanometre range. Instead, the description has to rely on a combination of mostly indirect methods. We then used the model to predict diffusion coefficients of water tracers, anions, and cations in a given clay. It is possible to obtain these coefficients in a consistent way for a single structural description, using input parameters derived from

  11. Computational study of the energetics of charge and cation mixing in U1-xCexO₂

    DOE PAGES

    Hanken, B. E.; Stanek, C. R.; Grønbech-Jensen, N.; Asta, M.

    2011-08-26

    The formalism of electronic density-functional theory (DFT), with Hubbard-U corrections (DFT+U), is employed in a computational study of the energetics of fluorite-structured U1-xCexO₂ mixtures. The computational approach makes use of a procedure which facilitates convergence of the calculations to multiple self-consistent DFT+U solutions for a given cation arrangement, corresponding to different charge states for the U and Ce ions in several prototypical cation arrangements. Results indicate a significant dependence of the structural and energetic properties on the nature of both charge and cation ordering. With the effective Hubbard-U parameters that reproduce well the measured oxidation-reduction energies for urania and ceria,more » we find that charge transfer between U⁴⁺ and Ce⁴⁺ ions, leading to the formation of U⁵⁺ and Ce³⁺, gives rise to an increase in the mixing energy in the range of 4–14 kJ/mol of the formula unit, depending on the nature of the cation ordering. The results suggest that although charge transfer between uranium and cerium ions is disfavored energetically, it is likely to be entropically stabilized at the high temperatures relevant to the processing and service of urania-based solid solutions.« less

  12. Boron bridging of rhamnogalacturonan-II is promoted in vitro by cationic chaperones, including polyhistidine and wall glycoproteins.

    PubMed

    Chormova, Dimitra; Fry, Stephen C

    2016-01-01

    Dimerization of rhamnogalacturonan-II (RG-II) via boron cross-links contributes to the assembly and biophysical properties of the cell wall. Pure RG-II is efficiently dimerized by boric acid (B(OH)3 ) in vitro only if nonbiological agents for example Pb(2+) are added. By contrast, newly synthesized RG-II domains dimerize very rapidly in vivo. We investigated biological agents that might enable this. We tested for three such agents: novel enzymes, borate-transferring ligands and cationic 'chaperones' that facilitate the close approach of two polyanionic RG-II molecules. Dimerization was monitored electrophoretically. Parsley shoot cell-wall enzymes did not affect RG-II dimerization in vitro. Borate-binding ligands (apiose, dehydroascorbic acid, alditols) and small organic cations (including polyamines) also lacked consistent effects. Polylysine bound permanently to RG-II, precluding electrophoretic analysis. However, another polycation, polyhistidine, strongly promoted RG-II dimerization by B(OH)3 without irreversible polyhistidine-RG-II complexation. Likewise, partially purified spinach extensins (histidine/lysine-rich cationic glycoproteins), strongly promoted RG-II dimerization by B(OH)3 in vitro. Thus certain polycations, including polyhistidine and wall glycoproteins, can chaperone RG-II, manoeuvring this polyanionic polysaccharide domain such that boron-bridging is favoured. These chaperones dissociate from RG-II after facilitating its dimerization, indicating that they act catalytically rather than stoichiometrically. We propose a natural role for extensin-RG-II interaction in steering cell-wall assembly. PMID:26301520

  13. Boron bridging of rhamnogalacturonan-II is promoted in vitro by cationic chaperones, including polyhistidine and wall glycoproteins.

    PubMed

    Chormova, Dimitra; Fry, Stephen C

    2016-01-01

    Dimerization of rhamnogalacturonan-II (RG-II) via boron cross-links contributes to the assembly and biophysical properties of the cell wall. Pure RG-II is efficiently dimerized by boric acid (B(OH)3 ) in vitro only if nonbiological agents for example Pb(2+) are added. By contrast, newly synthesized RG-II domains dimerize very rapidly in vivo. We investigated biological agents that might enable this. We tested for three such agents: novel enzymes, borate-transferring ligands and cationic 'chaperones' that facilitate the close approach of two polyanionic RG-II molecules. Dimerization was monitored electrophoretically. Parsley shoot cell-wall enzymes did not affect RG-II dimerization in vitro. Borate-binding ligands (apiose, dehydroascorbic acid, alditols) and small organic cations (including polyamines) also lacked consistent effects. Polylysine bound permanently to RG-II, precluding electrophoretic analysis. However, another polycation, polyhistidine, strongly promoted RG-II dimerization by B(OH)3 without irreversible polyhistidine-RG-II complexation. Likewise, partially purified spinach extensins (histidine/lysine-rich cationic glycoproteins), strongly promoted RG-II dimerization by B(OH)3 in vitro. Thus certain polycations, including polyhistidine and wall glycoproteins, can chaperone RG-II, manoeuvring this polyanionic polysaccharide domain such that boron-bridging is favoured. These chaperones dissociate from RG-II after facilitating its dimerization, indicating that they act catalytically rather than stoichiometrically. We propose a natural role for extensin-RG-II interaction in steering cell-wall assembly.

  14. Tungsten diffusion in silicon

    SciTech Connect

    De Luca, A.; Texier, M.; Burle, N.; Oison, V.; Pichaud, B.; Portavoce, A.; Grosjean, C.

    2014-01-07

    Two doses (10{sup 13} and 10{sup 15} cm{sup −2}) of tungsten (W) atoms were implanted in different Si(001) wafers in order to study W diffusion in Si. The samples were annealed or oxidized at temperatures between 776 and 960 °C. The diffusion profiles were measured by secondary ion mass spectrometry, and defect formation was studied by transmission electron microscopy and atom probe tomography. W is shown to reduce Si recrystallization after implantation and to exhibit, in the temperature range investigated, a solubility limit close to 0.15%–0.2%, which is higher than the solubility limit of usual metallic impurities in Si. W diffusion exhibits unusual linear diffusion profiles with a maximum concentration always located at the Si surface, slower kinetics than other metals in Si, and promotes vacancy accumulation close to the Si surface, with the formation of hollow cavities in the case of the higher W dose. In addition, Si self-interstitial injection during oxidation is shown to promote W-Si clustering. Taking into account these observations, a diffusion model based on the simultaneous diffusion of interstitial W atoms and W-Si atomic pairs is proposed since usual models used to model diffusion of metallic impurities and dopants in Si cannot reproduce experimental observations.

  15. Tungsten diffusion in olivine

    NASA Astrophysics Data System (ADS)

    Cherniak, D. J.; Van Orman, J. A.

    2014-03-01

    Diffusion of tungsten has been characterized in synthetic forsterite and natural olivine (Fo90) under dry conditions. The source of diffusant was a mixture of magnesium tungstate and olivine powders. Experiments were prepared by sealing the source material and polished olivine under vacuum in silica glass ampoules with solid buffers to buffer at NNO or IW. Prepared capsules were annealed in 1 atm furnaces for times ranging from 45 min to several weeks, at temperatures from 1050 to 1450 °C. Tungsten distributions in the olivine were profiled by Rutherford Backscattering Spectrometry (RBS). The following Arrhenius relation is obtained for W diffusion in forsterite: D=1.0×10-8exp(-365±28 kJ mol/RT) m s Diffusivities for the synthetic forsterite and natural Fe-bearing olivine are similar, and tungsten diffusion in olivine shows little dependence on crystallographic orientation or oxygen fugacity. The slow diffusivities measured for W in olivine indicate that Hf-W ages in olivine-metal systems will close to diffusive exchange at higher temperatures than other chronometers commonly used in cosmochronology, and that tungsten isotopic signatures will be less likely to be reset by subsequent thermal events.

  16. Solution of the nonlinear Poisson-Boltzmann equation: Application to ionic diffusion in cementitious materials

    SciTech Connect

    Arnold, J.; Kosson, D.S.; Garrabrants, A.; Meeussen, J.C.L.; Sloot, H.A. van der

    2013-02-15

    A robust numerical solution of the nonlinear Poisson-Boltzmann equation for asymmetric polyelectrolyte solutions in discrete pore geometries is presented. Comparisons to the linearized approximation of the Poisson-Boltzmann equation reveal that the assumptions leading to linearization may not be appropriate for the electrochemical regime in many cementitious materials. Implications of the electric double layer on both partitioning of species and on diffusive release are discussed. The influence of the electric double layer on anion diffusion relative to cation diffusion is examined.

  17. Diffusion Flame Stabilization

    NASA Technical Reports Server (NTRS)

    Takahashi, Fumiaki; Katta, V. R.

    2006-01-01

    Diffusion flames are commonly used for industrial burners in furnaces and flares. Oxygen/fuel burners are usually diffusion burners, primarily for safety reasons, to prevent flashback and explosion in a potentially dangerous system. Furthermore, in most fires, condensed materials pyrolyze, vaporize, and burn in air as diffusion flames. As a result of the interaction of a diffusion flame with burner or condensed-fuel surfaces, a quenched space is formed, thus leaving a diffusion flame edge, which plays an important role in flame holding in combustion systems and fire spread through condensed fuels. Despite a long history of jet diffusion flame studies, lifting/blowoff mechanisms have not yet been fully understood, compared to those of premixed flames. In this study, the structure and stability of diffusion flames of gaseous hydrocarbon fuels in coflowing air at normal earth gravity have been investigated experimentally and computationally. Measurements of the critical mean jet velocity (U(sub jc)) of methane, ethane, or propane at lifting or blowoff were made as a function of the coflowing air velocity (U(sub a)) using a tube burner (i.d.: 2.87 mm). By using a computational fluid dynamics code with 33 species and 112 elementary reaction steps, the internal chemical-kinetic structures of the stabilizing region of methane and propane flames were investigated. A peak reactivity spot, i.e., reaction kernel, is formed in the flame stabilizing region due to back-diffusion of heat and radical species against an oxygen-rich incoming flow, thus holding the trailing diffusion flame. The simulated flame base moved downstream under flow conditions close to the measured stability limit.

  18. Diffusion Flame Stabilization

    NASA Technical Reports Server (NTRS)

    Takahashi, Fumiaki; Katta, Viswanath R.

    2007-01-01

    Diffusion flames are commonly used for industrial burners in furnaces and flares. Oxygen/fuel burners are usually diffusion burners, primarily for safety reasons, to prevent flashback and explosion in a potentially dangerous system. Furthermore, in most fires, condensed materials pyrolyze, vaporize, and burn in air as diffusion flames. As a result of the interaction of a diffusion flame with burner or condensed-fuel surfaces, a quenched space is formed, thus leaving a diffusion flame edge, which plays an important role in flame holding in combustion systems and fire spread through condensed fuels. Despite a long history of jet diffusion flame studies, lifting/blowoff mechanisms have not yet been fully understood, compared to those of premixed flames. In this study, the structure and stability of diffusion flames of gaseous hydrocarbon fuels in coflowing air at normal earth gravity have been investigated experimentally and computationally. Measurements of the critical mean jet velocity (U(sub jc)) of methane, ethane, or propane at lifting or blowoff were made as a function of the coflowing air velocity (U(sub a)) using a tube burner (i.d.: 2.87 mm) (Fig. 1, left). By using a computational fluid dynamics code with 33 species and 112 elementary reaction steps, the internal chemical-kinetic structures of the stabilizing region of methane and propane flames were investigated (Fig. 1, right). A peak reactivity spot, i.e., reaction kernel, is formed in the flame stabilizing region due to back-diffusion of heat and radical species against an oxygen-rich incoming flow, thus holding the trailing diffusion flame. The simulated flame base moved downstream under flow conditions close to the measured stability limit.

  19. Something from nothing: enhancing electrochemical charge storage with cation vacancies.

    PubMed

    Hahn, Benjamin P; Long, Jeffrey W; Rolison, Debra R

    2013-05-21

    The performance of electrochemical energy storage devices (e.g., batteries and electrochemical capacitors) is largely determined by the physicochemical properties of the active electrode materials, such as the thermodynamic potential associated with the charge-storage reaction, ion-storage capacity, and long-term electrochemical stability. In the case of mixed ion/electron-conducting metal oxides that undergo cation-insertion reactions, the presence of cation vacancies in the lattice structure can enhance one or more of these technical parameters without resorting to a drastic change in material composition. Examples of this enhancement include the charge-storage properties of certain cation-deficient oxides such as γ-MnO2 and γ-Fe2O3 relative to their defect-free analogues. The optimal cation-vacancy fraction is both material- and application-dependent because cation vacancies enhance some materials properties at the expense of others, potentially affecting electronic conductivity or thermal stability. Although the advantages of structural cation vacancies have been known since at least the mid-1980s, only a handful of research groups have purposefully integrated cation vacancies into active electrode materials to enhance device performance. Three protocols are available for the incorporation of cation vacancies into transition metal oxides to improve performance in both aqueous and nonaqueous energy storage. Through a processing approach, researchers induce point defects in conventional oxides using traditional solid-state-ionics techniques that treat the oxide under appropriate atmospheric conditions with a driving force such as temperature. In a synthetic approach, substitutional doping of a highly oxidized cation into a metal-oxide framework can significantly increase cation-vacancy content and corresponding charge-storage capacity. In a scaling approach, electrode materials that are expressed in morphologies with high surface areas, such as aerogels

  20. Determining diffusion coefficients of ionic liquids by means of field cycling nuclear magnetic resonance relaxometry

    NASA Astrophysics Data System (ADS)

    Kruk, D.; Meier, R.; Rachocki, A.; Korpała, A.; Singh, R. K.; Rössler, E. A.

    2014-06-01

    Field Cycling Nuclear Magnetic Resonance (FC NMR) relaxation studies are reported for three ionic liquids: 1-ethyl-3- methylimidazolium thiocyanate (EMIM-SCN, 220-258 K), 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM-BF4, 243-318 K), and 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6, 258-323 K). The dispersion of 1H spin-lattice relaxation rate R1(ω) is measured in the frequency range of 10 kHz-20 MHz, and the studies are complemented by 19F spin-lattice relaxation measurements on BMIM-PF6 in the corresponding frequency range. From the 1H relaxation results self-diffusion coefficients for the cation in EMIM-SCN, BMIM-BF4, and BMIM-PF6 are determined. This is done by performing an analysis considering all relevant intra- and intermolecular relaxation contributions to the 1H spin-lattice relaxation as well as by benefiting from the universal low-frequency dispersion law characteristic of Fickian diffusion which yields, at low frequencies, a linear dependence of R1 on square root of frequency. From the 19F relaxation both anion and cation diffusion coefficients are determined for BMIM-PF6. The diffusion coefficients obtained from FC NMR relaxometry are in good agreement with results reported from pulsed- field-gradient NMR. This shows that NMR relaxometry can be considered as an alternative route of determining diffusion coefficients of both cations and anions in ionic liquids.

  1. Translational diffusion in mixtures of imidazolium ILs with polar aprotic molecular solvents.

    PubMed

    Marekha, Bogdan A; Kalugin, Oleg N; Bria, Marc; Buchner, Richard; Idrissi, Abdenacer

    2014-05-22

    Self-diffusion coefficients of cations and solvent molecules were determined with (1)H NMR in mixtures of 1-n-butyl-3-methylimidazolium (Bmim(+)) tetrafluoroborate (BF4(-)), hexafluorophosphate (PF6(-)), trifluoromethanesulfonate (TfO(-)), and bis(trifluoromethylsulfonyl)imide (TFSI(-)) with acetonitrile (AN), γ-butyrolactone (γ-BL), and propylene carbonate (PC) over the entire composition range at 300 K. The relative diffusivities of solvent molecules to cations as a function of concentration were found to depend on the solvent but not on the anion (i.e., IL). In all cases the values exhibit a plateau at low IL content (x(IL) < 0.2) and then increase steeply (AN), moderately (γ-BL), or negligibly (PC) at higher IL concentrations. This behavior was related to the different solvation patterns in the employed solvents. In BmimPF6-based systems, anionic diffusivities were followed via (31)P nuclei and found to be higher than the corresponding cation values in IL-poor systems and lower in the IL-rich region. The inversion point of relative ionic diffusivities was found around equimolar composition and does not depend on the solvent. At this point, a distinct change in the ion-diffusion mechanism appears to take place.

  2. Determining diffusion coefficients of ionic liquids by means of field cycling nuclear magnetic resonance relaxometry.

    PubMed

    Kruk, D; Meier, R; Rachocki, A; Korpała, A; Singh, R K; Rössler, E A

    2014-06-28

    Field Cycling Nuclear Magnetic Resonance (FC NMR) relaxation studies are reported for three ionic liquids: 1-ethyl-3- methylimidazolium thiocyanate (EMIM-SCN, 220-258 K), 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM-BF4, 243-318 K), and 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6, 258-323 K). The dispersion of (1)H spin-lattice relaxation rate R1(ω) is measured in the frequency range of 10 kHz-20 MHz, and the studies are complemented by (19)F spin-lattice relaxation measurements on BMIM-PF6 in the corresponding frequency range. From the (1)H relaxation results self-diffusion coefficients for the cation in EMIM-SCN, BMIM-BF4, and BMIM-PF6 are determined. This is done by performing an analysis considering all relevant intra- and intermolecular relaxation contributions to the (1)H spin-lattice relaxation as well as by benefiting from the universal low-frequency dispersion law characteristic of Fickian diffusion which yields, at low frequencies, a linear dependence of R1 on square root of frequency. From the (19)F relaxation both anion and cation diffusion coefficients are determined for BMIM-PF6. The diffusion coefficients obtained from FC NMR relaxometry are in good agreement with results reported from pulsed- field-gradient NMR. This shows that NMR relaxometry can be considered as an alternative route of determining diffusion coefficients of both cations and anions in ionic liquids.

  3. 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

  4. 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

  5. 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

  6. 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

  7. Ionization dynamics in ionic liquids probed via self-diffusion coefficient measurements

    NASA Astrophysics Data System (ADS)

    Mao, Yougang; Damodaran, Krishnan

    2014-08-01

    Ionic liquids contain ions and ion pairs with fast exchange between them. We propose a novel process to deduce the fraction of ions present in an ionic liquid and the equilibrium constants of ionization processes from measured ion self-diffusion coefficients using Pulsed Field Gradient (PFG) NMR. The enthalpy and entropy changes of ionization and ion self-diffusion processes are obtained for a series of ionic liquids using this method. These data were used to explain the interactions between cations and anions of ionic liquids. The interactions are also interpreted by the delocalization of the ion’s charge densities. The self-diffusion coefficients of cations and anions for measured ionic liquids are discussed.

  8. 50 CFR 17.107 - Facilitating enforcement.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... WILDLIFE AND PLANTS (CONTINUED) ENDANGERED AND THREATENED WILDLIFE AND PLANTS (CONTINUED) Manatee Protection Areas § 17.107 Facilitating enforcement. Water vehicles operating in manatee sanctuary or...

  9. 50 CFR 17.107 - Facilitating enforcement.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... WILDLIFE AND PLANTS (CONTINUED) ENDANGERED AND THREATENED WILDLIFE AND PLANTS (CONTINUED) Manatee Protection Areas § 17.107 Facilitating enforcement. Water vehicles operating in manatee sanctuary or...

  10. 50 CFR 17.107 - Facilitating enforcement.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... WILDLIFE AND PLANTS (CONTINUED) ENDANGERED AND THREATENED WILDLIFE AND PLANTS (CONTINUED) Manatee Protection Areas § 17.107 Facilitating enforcement. Water vehicles operating in manatee sanctuary or...

  11. 50 CFR 17.107 - Facilitating enforcement.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... WILDLIFE AND PLANTS (CONTINUED) ENDANGERED AND THREATENED WILDLIFE AND PLANTS (CONTINUED) Manatee Protection Areas § 17.107 Facilitating enforcement. Water vehicles operating in manatee sanctuary or...

  12. 50 CFR 17.107 - Facilitating enforcement.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... WILDLIFE AND PLANTS (CONTINUED) ENDANGERED AND THREATENED WILDLIFE AND PLANTS (CONTINUED) Manatee Protection Areas § 17.107 Facilitating enforcement. Water vehicles operating in manatee sanctuary or...

  13. Simple scale interpolator facilitates reading of graphs

    NASA Technical Reports Server (NTRS)

    Fetterman, D. E., Jr.

    1965-01-01

    Simple transparent overlay with interpolation scale facilitates accurate, rapid reading of graph coordinate points. This device can be used for enlarging drawings and locating points on perspective drawings.

  14. Lipopolysaccharide Neutralization by Cationic-Amphiphilic Polymers through Pseudoaggregate Formation.

    PubMed

    Uppu, Divakara S S M; Haldar, Jayanta

    2016-03-14

    Synthetic polymers incorporating the cationic charge and hydrophobicity to mimic the function of antimicrobial peptides (AMPs) have been developed. These cationic-amphiphilic polymers bind to bacterial membranes that generally contain negatively charged phospholipids and cause membrane disintegration resulting in cell death; however, cationic-amphiphilic antibacterial polymers with endotoxin neutralization properties, to the best of our knowledge, have not been reported. Bacterial endotoxins such as lipopolysaccharide (LPS) cause sepsis that is responsible for a great amount of mortality worldwide. These cationic-amphiphilic polymers can also bind to negatively charged and hydrophobic LPS and cause detoxification. Hence, we envisaged that cationic-amphiphilic polymers can have both antibacterial as well as LPS binding properties. Here we report synthetic amphiphilic polymers with both antibacterial as well as endotoxin neutralizing properties. Levels of proinflammatory cytokines in human monocytes caused by LPS stimulation were inhibited by >80% when coincubated with these polymers. These reductions were found to be dependent on concentration and, more importantly, on the side-chain chemical structure due to variations in the hydrophobicity profiles of these polymers. These cationic-amphiphilic polymers bind and cause LPS neutralization and detoxification. Investigations of polymer interaction with LPS using fluorescence spectroscopy and dynamic light scattering (DLS) showed that these polymers bind but neither dissociate nor promote LPS aggregation. We show that polymer binding to LPS leads to sort of a pseudoaggregate formation resulting in LPS neutralization/detoxification. These findings provide an unusual mechanism of LPS neutralization using novel synthetic cationic-amphiphilic polymers.

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

    PubMed

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

    2015-02-01

    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.

  16. Fouling mitigation in membrane bioreactors using multivalent cations.

    PubMed

    Mehrnia, Mohammad Reza; Azami, Hamed; Sarrafzadeh, Mohammad Hossein

    2013-09-01

    Several cations have been used to study the effect of mineral coagulants on activated sludge properties and membrane fouling in submerged membrane bioreactors (MBRs). The flocculability and settling properties of activated sludge were studied in various concentrations of sodium, potassium, magnesium, calcium, ferrum (in Fe(3+) form), and aluminum. Significant effect of cations and their concentrations on different parameters have been analyzed by 2-way ANOVA. Results showed that multivalent cations induce flocculation in bioreactors while monovalent cations have a detrimental effect on flocculability of activated sludge. The ratio of tight bound extracellular polymeric substances (TB-EPSs) to loosely bound (LB-EPSs) increased with concentration of multivalent cations that was in accordance with enhancement of biosorption in high concentration of multivalent cations. Moreover, these cations improved the settleability and dewatering properties of activated sludge. They also mitigated membrane fouling in the MBRs so that calcium and aluminum reduced membrane fouling to nearly 30%. Simple but useful correlations were developed for description of activated sludge properties based on easy measurable parameters that could be used also for estimation of membrane fouling. It was found that the ratio of TB-EPS to LB-EPS and also flocs size distribution are the main parameters affecting membrane fouling.

  17. Spatial facilitation and depression within one motor nerve terminal of frogs.

    PubMed Central

    Dudel, J; Parnas, I; Parnas, H

    1993-01-01

    1. Perfused macropatch electrodes were used to stimulate and simultaneously measure release from two sites on the same terminal of the frog cutaneous pectoris muscle. 2. It was found that release occurring at one site often affected release at an adjacent site 50 microns away, either enhancing it ('spatial facilitation') or depressing it ('spatial depression'). Spatial facilitation (or depression) was defined as the release produced by a test pulse at the second site (test electrode) when preceded by a pulse at the first site (prepulse electrode) divided by the release produced by the test pulse alone. 3. Spatial facilitation varied with the time interval between the prepulse and the test pulse. Peak spatial facilitation, which on the average was 2.14, occurred with an interval of 1-3 ms. With longer intervals spatial facilitation decayed with a time constant between 3-6 ms. When the time interval between the prepulse and the test pulse was zero (no delay), the release after the test pulse was always depressed. 4. When Ca2+ was omitted from the perfusate of the prepulse electrode, spatial facilitation was abolished. When a brief hyperpolarizing pulse followed the depolarizing prepulse with zero delay spatial facilitation was also abolished. 5. Electrotonic spread or Ca2+ diffusion within the axon terminal are excluded as coupling agents for spatial facilitation. It is suggested that the coupling agent may possibly be related to a hypothetical release-promoting factor. Images Fig. 1 PMID:8350260

  18. Hereditary Diffuse Gastric Cancer

    MedlinePlus

    ... with the syndrome is recommended. What are the estimated cancer risks associated with HDGC? Not everyone who ... the lifetime risk for diffuse gastric cancer is estimated to be 70% to 80% for men and ...

  19. Multinomial Diffusion Equation

    SciTech Connect

    Balter, Ariel I.; Tartakovsky, Alexandre M.

    2011-06-01

    We have developed a novel stochastic, space/time discrete representation of particle diffusion (e.g. Brownian motion) based on discrete probability distributions. We show that in the limit of both very small time step and large concentration, our description is equivalent to the space/time continuous stochastic diffusion equation. Being discrete in both time and space, our model can be used as an extremely accurate, efficient, and stable stochastic finite-difference diffusion algorithm when concentrations are so small that computationally expensive particle-based methods are usually needed. Through numerical simulations, we show that our method can generate realizations that capture the statistical properties of particle simulations. While our method converges converges to both the correct ensemble mean and ensemble variance very quickly with decreasing time step, but for small concentration, the stochastic diffusion PDE does not, even for very small time steps.

  20. Lung diffusion testing

    MedlinePlus

    Lung diffusion testing measures how well the lungs exchange gases. This is an important part of lung testing , because ... gases do not move normally across the lung tissues into the blood vessels of the lung. This ...

  1. Investigating diffusion with technology

    NASA Astrophysics Data System (ADS)

    Miller, Jon S.; Windelborn, Augden F.

    2013-07-01

    The activities described here allow students to explore the concept of diffusion with the use of common equipment such as computers, webcams and analysis software. The procedure includes taking a series of digital pictures of a container of water with a webcam as a dye slowly diffuses. At known time points, measurements of the pixel densities (darkness) of the digital pictures are recorded and then plotted on a graph. The resulting graph of darkness versus time allows students to see the results of diffusion of the dye over time. Through modification of the basic lesson plan, students are able to investigate the influence of a variety of variables on diffusion. Furthermore, students are able to expand the boundaries of their thinking by formulating hypotheses and testing their hypotheses through experimentation. As a result, students acquire a relevant science experience through taking measurements, organizing data into tables, analysing data and drawing conclusions.

  2. Cations bind only weakly to amides in aqueous solutions.

    PubMed

    Okur, Halil I; Kherb, Jaibir; Cremer, Paul S

    2013-04-01

    We investigated salt interactions with butyramide as a simple mimic of cation interactions with protein backbones. The experiments were performed in aqueous metal chloride solutions using two spectroscopic techniques. In the first, which provided information about contact pair formation, the response of the amide I band to the nature and concentration of salt was monitored in bulk aqueous solutions via attenuated total reflection Fourier transform infrared spectroscopy. It was found that molar concentrations of well-hydrated metal cations (Ca(2+), Mg(2+), Li(+)) led to the rise of a peak assigned to metal cation-bound amides (1645 cm(-1)) and a decrease in the peak associated with purely water-bound amides (1620 cm(-1)). In a complementary set of experiments, the effect of cation identity and concentration was investigated at the air/butyramide/water interface via vibrational sum frequency spectroscopy. In these studies, metal ion-amide binding led to the ordering of the adjacent water layer. Such experiments were sensitive to the interfacial partitioning of cations in either a contact pair with the amide or as a solvent separated pair. In both experiments, the ordering of the interactions of the cations was: Ca(2+) > Mg(2+) > Li(+) > Na(+) ≈ K(+). This is a direct cationic Hofmeister series. Even for Ca(2+), however, the apparent equilibrium dissociation constant of the cation with the amide carbonyl oxygen was no tighter than ∼8.5 M. For Na(+) and K(+), no evidence was found for any binding. As such, the interactions of metal cations with amides are far weaker than the analogous binding of weakly hydrated anions.

  3. Trace-Element Diffusion Coefficients in Olivine

    NASA Astrophysics Data System (ADS)

    Spandler, C.; O'Neill, H. S.

    2006-12-01

    We have undertaken chemical diffusion experiments at 1300°C to determine both crystal/melt partition coefficients and diffusion coefficients for a wide range of trace elements in forsteritic olivine. Experiments were conducted at 1 atm under controlled fO2 for up to 25 days using synthetic melts made to a composition in equilibrium with olivine for major elements, and doped with selected trace elements. The melt was put into a 5 mm diameter cylindrical hole in gem quality San Carlos olivine crystals drilled paralell to the a axis. Diffusion profiles were obtained both for trace elements that were added to the starting material and diffuse into the olivine, and also for several trace elements present at natural abundances in the olivine that diffuse out. The profiles were measured across sections perpendicular to crystal/melt boundary at a variety of crystallographic orientations (confirmed by EBSD) by laser-ablation ICP-MS. A thin laser slit oriented parallel to the crystal/melt interface was traversed from the melt through the crystal. Element concentrations were fitted to the diffusion equation to obtain both diffusion coefficients and concentrations at the crystal/melt interface, and hence partition coefficients. Calculated diffusivities for many trace elements (Ca, REE, Y, Sc, V, Cr, Ni, Co, Mn, Na, Li, Be, Ti) are relatively fast (D = 10-16 to 10^{-13 m2/s at 1300°C). The diffusion of Li in olivine (approx. D = 10^{-15} m2/s) is only slightly slower than REEs and similar to divalent cations, in good agreement with inferences from zoning profiles in natural olivine [1]. This rate is considerably slower than for plagioclase and clinopyroxene [2], a result which has important implications for interpreting Li isotopic data from mantle-derived rocks. The fastest diffusing trace element we observe is Be. Applying our diffusion and partition coefficients to the model of Qin et al. [3], we calculate that the REEs of olivine-hosted melt inclusions in the mantle will

  4. Hydrogen Diffusion in Forsterite

    NASA Astrophysics Data System (ADS)

    Demouchy, S.; Mackwell, S.

    2002-12-01

    Physical and chemical properties of Earth's mantle are readily modified by interaction with volatiles, such as water. Thus, characterization of solubility and kinetics of incorporation for water in nominally anhydrous minerals is important in order to understand the behavior of Earth's interior under hydrous conditions. Experimental studies on the olivine-water system indicate that significant amounts of OH can dissolve within olivine as point defects (Bell and Rossman, 1992; Kohlstedt et al. 1996). Extending Kohlstedt and Mackwell's (1998) work, our study concerns the kinetics of hydrogen transport in the iron-free olivine-water system. This study is based on hydrogenation of forsterite samples during piston-cylinder and TZM cold-seal vessel experiments. We use infrared analyses in order to constrain the speciation of the mobile water-derived defects in forsterite single-crystal sample, and the rates of diffusion of such species under uppermost mantle conditions (0.2 to 1.5 GPa, 900 to 1100° C). Hydrogen defect transport in single crystals of forsterite is investigated for diffusion parallel to each crystallographic axis. Defect diffusivities are obtained by fitting a diffusion law to the OH content as a function of position in the sample. Our current results indicate that incorporation of hydroxyl species into iron-free olivine is a one-stage process with hydrogen diffusion linked to magnesium vacancy self-diffusion DV, such that DV = D~/3 = 10-12 m2/s at 1000° C parallel to [001], where D~ represents the chemical diffusivity. Those diffusion rates are slightly lower than in iron-bearing olivine for the same incorporation mechanism. The different concentration profiles show a clear anisotropy of diffusion, with fastest diffusion parallel to [001] as in iron-bearing olivine. Thus, while hydrogen solubilities are dependent on iron content, the rate of incorporation of water-derived species in olivine is not strongly coupled to the concentration of iron. This

  5. Using learning theory, interprofessional facilitation competencies, and behavioral indicators to evaluate facilitator training.

    PubMed

    LeGros, Theresa A; Amerongen, Helen M; Cooley, Janet H; Schloss, Ernest P

    2015-01-01

    Despite the increasing need for faculty and preceptors skilled in interprofessional facilitation (IPF), the relative novelty of the field poses a challenge to the development and evaluation of IPF programs. We use learning theory and IPF competencies with associated behavioral indicators to develop and evaluate six key messages in IPF training and experience. Our mixed methods approach included two phases: quantitative data collection with embedded qualitative data, followed by qualitative data collection in explanatory sequential fashion. This enabled triangulated analyses of both data types and of facilitation behaviors from facilitator and student perspectives. Results indicate the competency-based training was effective. Facilitators felt comfortable performing behaviors associated with IPF competencies; student observations of those behaviors supported facilitator self-reported performance. Overall, students perceived more facilitation opportunities than facilitators. Findings corroborate the importance of recruiting seasoned facilitators and establishing IPF guidelines that acknowledge variable team dynamics and help facilitators recognize teachable moments. PMID:26230378

  6. Using learning theory, interprofessional facilitation competencies, and behavioral indicators to evaluate facilitator training.

    PubMed

    LeGros, Theresa A; Amerongen, Helen M; Cooley, Janet H; Schloss, Ernest P

    2015-01-01

    Despite the increasing need for faculty and preceptors skilled in interprofessional facilitation (IPF), the relative novelty of the field poses a challenge to the development and evaluation of IPF programs. We use learning theory and IPF competencies with associated behavioral indicators to develop and evaluate six key messages in IPF training and experience. Our mixed methods approach included two phases: quantitative data collection with embedded qualitative data, followed by qualitative data collection in explanatory sequential fashion. This enabled triangulated analyses of both data types and of facilitation behaviors from facilitator and student perspectives. Results indicate the competency-based training was effective. Facilitators felt comfortable performing behaviors associated with IPF competencies; student observations of those behaviors supported facilitator self-reported performance. Overall, students perceived more facilitation opportunities than facilitators. Findings corroborate the importance of recruiting seasoned facilitators and establishing IPF guidelines that acknowledge variable team dynamics and help facilitators recognize teachable moments.

  7. Theoretical study of electronically excited radical cations of naphthalene and anthracene as archetypal models for astrophysical observations. Part I. Static aspects.

    PubMed

    Ghanta, S; Reddy, V Sivaranjana; Mahapatra, S

    2011-08-28

    Motivated by the recent discovery of new diffuse interstellar bands and results from laboratory experiments, ab initio quantum chemistry calculations are carried out for the lowest six electronic states of naphthalene and anthracene radical cations. The calculated adiabatic electronic energies are utilized to construct suitable diabatic electronic Hamiltonians in order to perform nuclear dynamics studies in Part II. Complex entanglement of the electronic states is established for both the radical cations and the coupling surfaces among them are also derived in accordance with the symmetry selection rules. Critical examination of the coupling parameters of the Hamiltonian suggests that 29 (out of 48) and 31 (out of 66) vibrational modes are relevant in the nuclear dynamics in the six lowest electronic states of naphthalene and anthracene radical cations, respectively. PMID:21750790

  8. Nodal Diffusion & Transport Theory

    1992-02-19

    DIF3D solves multigroup diffusion theory eigenvalue, adjoint, fixed source, and criticality (concentration, buckling, and dimension search) problems in 1, 2, and 3-space dimensions for orthogonal (rectangular or cylindrical), triangular, and hexagonal geometries. Anisotropic diffusion theory coefficients are permitted. Flux and power density maps by mesh cell and regionwise balance integrals are provided. Although primarily designed for fast reactor problems, upscattering and internal black boundary conditions are also treated.

  9. Infrared Spectroscopic Study for the Hydrated Clusters of Pentane Cation

    NASA Astrophysics Data System (ADS)

    Endo, Tomoya; Matsuda, Yoshiyuki; Fujii, Asuka

    2016-06-01

    We performed infrared predissociation spectroscopy of size-selected pentane-water cluster cations, [pentane-(H2O)n]+, n=1-3, generated through the vacuum-ultraviolet photoionization. In the infrared spectra of the di- and tri-hydrated clusters, there appear broad features which spread to the lower frequency region from 2800 cm-1. These broad features are assigned to vibrations of a proton, which is transferred from CH of the pentane cation to the water molecules. These results indicate that the pentane cation has high proton donor ability. We will discuss these results based on theoretical conputations.

  10. High affinity of water-soluble cryptophanes for cesium cations.

    PubMed

    Brotin, Thierry; Montserret, Roland; Bouchet, Aude; Cavagnat, Dominique; Linares, Mathieu; Buffeteau, Thierry

    2012-01-20

    Exceptionally high affinity for cesium cations was achieved in aqueous solution using two enantiopure cryptophanes. Complexation of cesium was evidenced by (133)Cs NMR spectroscopy and by electronic circular dichroism (ECD). Binding constants as high as 6 × 10(9) M(-1) have been measured by isothermal titration calorimetry (ITC). Very strong complexation of rubidium cations (K ~10(6) M(-1)) has also been measured. Chiral hosts allowed the detection of the two cations at low concentrations (μM) using ECD.

  11. 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

  12. 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.

  13. 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.

  14. Advanced manufacturing: Technology diffusion

    SciTech Connect

    Tesar, A.

    1995-12-01

    In this paper we examine how manufacturing technology diffuses rom the developers of technology across national borders to those who do not have the capability or resources to develop advanced technology on their own. None of the wide variety of technology diffusion mechanisms discussed in this paper are new, yet the opportunities to apply these mechanisms are growing. A dramatic increase in technology diffusion occurred over the last decade. The two major trends which probably drive this increase are a worldwide inclination towards ``freer`` markets and diminishing isolation. Technology is most rapidly diffusing from the US In fact, the US is supplying technology for the rest of the world. The value of the technology supplied by the US more than doubled from 1985 to 1992 (see the Introduction for details). History shows us that technology diffusion is inevitable. It is the rates at which technologies diffuse to other countries which can vary considerably. Manufacturers in these countries are increasingly able to absorb technology. Their manufacturing efficiency is expected to progress as technology becomes increasingly available and utilized.

  15. Unsteady planar diffusion flames: Ignition, travel, burnout

    NASA Technical Reports Server (NTRS)

    Fendell, F.; Wu, F.

    1995-01-01

    In microgravity, a thin planar diffusion flame is created and thenceforth travels so that the flame is situated at all times at an interface at which the hydrogen and oxygen meet in stoichiometric proportion. If the initial amount of hydrogen is deficient relative to the initial amount of oxygen, then the planar flame will travel further and further into the half volume initially containing hydrogen, until the hydrogen is (virtually) fully depleted. Of course, when the amount of residual hydrogen becomes small, the diffusion flame is neither vigorous nor thin; in practice, the flame is extinguished before the hydrogen is fully depleted, owing to the finite rate of the actual chemical-kinetic mechanism. The rate of travel of the hydrogen-air diffusion flame is much slower than the rate of laminar flame propagation through a hydrogen-air mixture. This slow travel facilitates diagnostic detection of the flame position as a function of time, but the slow travel also means that the time to burnout (extinction) probably far exceeds the testing time (typically, a few seconds) available in earth-sited facilities for microgravity-environment experiments. We undertake an analysis to predict (1) the position and temperature of the diffusion flame as a function of time, (2) the time at which extinction of the diffusion flame occurs, and (3) the thickness of quench layers formed on side walls (i.e., on lateral boundaries, with normal vectors parallel to the diffusion-flame plane), and whether, prior to extinction, water vapor formed by burning will condense on these cold walls.

  16. Calcium diffusion enhanced after cleavage of negatively charged components of brain extracellular matrix by chondroitinase ABC

    PubMed Central

    Hrabětová, Sabina; Masri, Daniel; Tao, Lian; Xiao, Fanrong; Nicholson, Charles

    2009-01-01

    The concentration of extracellular calcium plays a critical role in synaptic transmission and neuronal excitability as well as other physiological processes. The time course and extent of local fluctuations in the concentration of this ion largely depend on its effective diffusion coefficient (D*) and it has been speculated that fixed negative charges on chondroitin sulphate proteoglycans (CSPGs) and other components of the extracellular matrix may influence calcium diffusion because it is a divalent cation. In this study we used ion-selective microelectrodes combined with pressure ejection or iontophoresis of ions from a micropipette to quantify diffusion characteristics of neocortex and hippocampus in rat brain slices. We show that D* for calcium is less than the value predicted from the behaviour of the monovalent cation tetramethylammonium (TMA), a commonly used diffusion probe, but D* for calcium increases in both brain regions after the slices are treated with chondroitinase ABC, an enzyme that predominantly cleaves chondroitin sulphate glycans. These results suggest that CSPGs do play a role in determining the local diffusion properties of calcium in brain tissue, most likely through electrostatic interactions mediating rapid equilibrium binding. In contrast, chondroitinase ABC does not affect either the TMA diffusion or the extracellular volume fraction, indicating that the enzyme does not alter the structure of the extracellular space and that the diffusion of small monovalent cations is not affected by CSPGs in the normal brain ionic milieu. Both calcium and CSPGs are known to have many distinct roles in brain physiology, including brain repair, and our study suggests they may be functionally coupled through calcium diffusion properties. PMID:19546165

  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. Cation-exchange chromatography of monoclonal antibodies

    PubMed Central

    Urmann, Marina; Graalfs, Heiner; Joehnck, Matthias; Jacob, Lothar R

    2010-01-01

    A novel cation-exchange resin, Eshmuno™ S, was compared to Fractogel® SO3− (M) and Toyopearl GigaCap S-650M. The stationary phases have different base matrices and carry specific types of polymeric surface modifications. Three monoclonal antibodies (mAbs) were used as model proteins to characterize these chromatographic resins. Results from gradient elutions, stirred batch adsorptions and confocal laser scanning microscopic investigations were used to elucidate binding behavior of mAbs onto Eshmuno™ S and Fractogel® SO3− and the corresponding transport mechanisms on these two resins. The number of charges involved in mAb binding for Eshmuno™ S is lower than for Fractogel® SO3−, indicating a slightly weaker electrostatic interaction. Kinetics from batch uptake experiments are compared to kinetic data obtained from confocal laser scanning microscopy images. Both experimental approaches show an accelerated protein adsorption for the novel stationary phase. The influence of pH, salt concentrations and residence times on dynamic binding capacities was determined. A higher dynamic binding capacity for Eshmuno™ S over a wider range of pH values and residence times was found compared to Fractogel® SO3− and Toyopearl GigaCap S-650M. The capture of antibodies from cell culture supernatant, as well as post-protein A eluates, were analyzed with respect to their host cell protein (hcp) removal capabilities. Comparable or even better hcp clearance was observed at much higher protein loading for Eshmuno™ S than Fractogel® SO3− or Toyopearl GigaCap S-650M. PMID:20559022

  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. The Diffusion Process of Patient Education in Dutch Community Pharmacy: An Exploration.

    ERIC Educational Resources Information Center

    Pronk, M. C. M.; Blom, A. Th. G.; Van Burg, A.; Jonkers, R.

    2001-01-01

    Identifies barriers and facilitators to the implementation of patient education in community pharmacies and classifies these barriers and facilitators into the diffusion stages of Rogers'"Innovations in Organizations" model. Discusses the implementation of patient education activities that require individual and organizational change in…

  1. Influence of long-range cation order on relaxor properties of doped Pb(Mg1/3Nb2/3)O3 ceramics

    NASA Astrophysics Data System (ADS)

    Zhao, X.; Qu, W.; Tan, X.; Bokov, A. A.; Ye, Z.-G.

    2009-04-01

    The 1:1 B -site cation order in Pb(Mg1/3Nb2/3)O3 relaxor ferroelectric ceramics was significantly enhanced by doping of minor amounts of La3+ , Sc3+ , or W6+ (less than 3at.% ) combined with a slow cooling procedure. Transmission electron microscopy examination confirmed the size increase of the cation-ordered regions embedded in a disordered matrix in the samples that were slowly cooled after sintering. The average cation ordering parameter (S) determined from x-ray diffraction data in these partially ordered samples was about 0.3-0.4. The ferroelectric properties and dielectric relaxation were compared in partially ordered and disordered (S=0) samples with the same composition. It was found that typical relaxor behavior was preserved in partially ordered ceramics. Furthermore, the temperature and diffuseness of the characteristic relaxor permittivity peak and the parameters of dielectric relaxation (in particular, the distribution of relaxation times and the Vogel-Fulcher freezing temperature) were practically independent of S . In contrast, the diffuseness of the phase transition from the ferroelectric phase (induced by external electric field) to the ergodic relaxor phase appeared to be much larger in the disordered samples than in the partially ordered ones (this diffuseness was assessed using pyroelectric current and ferroelectric hysteresis loops). These results suggest that cation ordering did not influence the behavior of polar nanoregions which are responsible for the dielectric response in the ergodic relaxor phase but significantly influenced the ferroelectric phase transition. The results are interpreted in terms of different types of polar regions in the disordered matrix and cation-ordered domains.

  2. "Stepping Up": A Focus on Facilitator Development

    ERIC Educational Resources Information Center

    Kostouros, Patricia; Warthe, D. Gaye; Carter-Snell, Catherine; Burnett, Che

    2016-01-01

    This article examines the impact on peer facilitators in "Stepping Up," a dating violence prevention program at a Canadian university. A focus group held eight months following the delivery of the program determined the personal impact of involvement in the program. Results indicate that peer facilitators experienced personal growth as…

  3. Peervention: Training Peer Facilitators for Prevention Education.

    ERIC Educational Resources Information Center

    Myrick, Robert D.; Folk, Betsy E.

    This book introduces students to the helping relationship and appropriate methods of responding to others through a variety of experiential training activities. The first chapter discusses the need for peer facilitators. The peer facilitator movement is traced to the 1970s, and the power of peer relationships is described. Four basic helping roles…

  4. Parent Involvement Facilitators: Unlocking Social Capital Wealth

    ERIC Educational Resources Information Center

    Ferrara, Margaret M.

    2015-01-01

    This case study provides an overview of a family outreach intervention that supports student retention in school through a school-home communication link. This intervention structure, which employs staff appropriately called parent involvement facilitators (PIFs), is one that school districts have employed to facilitate family engagement in…

  5. Facilitated Communication: The Clinical and Social Phenomenon.

    ERIC Educational Resources Information Center

    Shane, Howard C., Ed.

    This text explains the phenomenon of facilitated communication (FC) from an empirical, data-based, and/or clinical perspective. It is not a how-to-facilitate text, but one that explores the clinical and sociological reality of FC. A common theme running through each of the papers in the book is the question of FC's legitimacy. The papers reveal…

  6. A Model of Small Group Facilitator Competencies

    ERIC Educational Resources Information Center

    Kolb, Judith A.; Jin, Sungmi; Song, Ji Hoon

    2008-01-01

    This study used small group theory, quantitative and qualitative data collected from experienced practicing facilitators at three points of time, and a building block process of collection, analysis, further collection, and consolidation to develop a model of small group facilitator competencies. The proposed model has five components:…

  7. 49 CFR 38.2 - Equivalent facilitation.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 1 2010-10-01 2010-10-01 false Equivalent facilitation. 38.2 Section 38.2 Transportation Office of the Secretary of Transportation AMERICANS WITH DISABILITIES ACT (ADA) ACCESSIBILITY SPECIFICATIONS FOR TRANSPORTATION VEHICLES General § 38.2 Equivalent facilitation. Departures from...

  8. 75 FR 64641 - Facilitating Shareholder Director Nominations

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-10-20

    ... COMMISSION 17 CFR Parts 200, 232, 240, and 249 RIN 3235-AK27 Facilitating Shareholder Director Nominations... rules that the Commission adopted to facilitate the effective exercise of shareholders' traditional state law rights to nominate and elect directors to company boards of directors. We are publishing...

  9. Escaping Homelessness: Anticipated and Perceived Facilitators

    ERIC Educational Resources Information Center

    Patterson, Allisha; Tweed, Roger

    2009-01-01

    One study with two distinct sections was conducted to identify factors facilitating escape from homelessness. In Section 1, 58 homeless individuals rated possible facilitators of escape (factors they believed would help them become more independent and self-sufficient). In Section 2, 80 participants who had already exited homelessness rated the…

  10. A Multitask Controlled Evaluation of Facilitated Communication.

    ERIC Educational Resources Information Center

    Vazquez, Carol A.

    1994-01-01

    This study tested the validity of facilitated communication with 2 students (ages 10 and 12) with autism, using a picture identification task, video task, and object identification. Subjects were able to report information unknown to the facilitator in one out of four controlled sessions. Strong evidence for direct cuing between subject and…

  11. Facilitator's Manual: Summer Transitions. Fifth Edition.

    ERIC Educational Resources Information Center

    Kuenzli, Linda A., Ed.

    A facilitator's manual for the Summer Transition Enrichment Program at Bowling Green State University is presented. The overall objectives of the program are: (1) to facilitate the transition of entering freshmen into the academic and cultural life of the university; and (2) to assist students in their personal growth and adjustment to the…

  12. The Role of Touch in Facilitated Communication.

    ERIC Educational Resources Information Center

    Kezuka, Emiko

    1997-01-01

    A study investigated the role of touch in the use of facilitated communication with Japanese individuals with autism. Five experiments were conducted involving a "telepathy game" using a rod with an attached strain gauge. Results found the facilitator's contact controlled the motor responses of the subjects. (Author/CR)

  13. Toward Facilitative Mentoring and Catalytic Interventions

    ERIC Educational Resources Information Center

    Smith, Melissa K.; Lewis, Marilyn

    2015-01-01

    In TESOL teacher mentoring, giving advice can be conceptualized as a continuum, ranging from directive to facilitative feedback. The goal, over time, is to lead toward the facilitative end of the continuum and specifically to catalytic interventions that encourage self-reflection and autonomous learning. This study begins by examining research on…

  14. Reconceptualizing the Pedagogical Value of Student Facilitation

    ERIC Educational Resources Information Center

    Oztok, Murat

    2016-01-01

    Sustained discourse is critical to the learning potential of online courses. And, while research has surfaced many factors that mediate interaction, it further suggests that sustained interaction remains elusive. In this paper, I propose that student facilitation may have an impact on the quality of facilitators' interactions following a week of…

  15. A Dialogic Approach to Online Facilitation

    ERIC Educational Resources Information Center

    Swann, Jennie

    2010-01-01

    Social construction of understanding has long been a significant underlying principle of learning and teaching, and while there are many models for the design of online activities to promote this, there are considerably fewer models for the facilitation of such dialogue. This paper examines some of these facilitation models from the point of view…

  16. Social Facilitation: A Test of Two Theories.

    ERIC Educational Resources Information Center

    Ryujin, Donald H.; And Others

    Social facilitation can be defined as the effect of an audience or coactors on performance. Research on social facilitation effects has produced some contradictory and confusing findings. Some studies have found that the presence of others enhances performance; other studies have found that the presence of an audience or coactors impairs…

  17. Facilitator Talk in EAP Reading Classes

    ERIC Educational Resources Information Center

    Wilson, Kate

    2008-01-01

    Current sociocultural perspectives on language learning call on teachers to reinvent themselves in ways which facilitate student learning rather than transmit knowledge. For teachers, this means adopting new roles, and acquiring a new repertoire of teacher talk. This paper aims to further the work on facilitator talk begun by Clifton (2006) and…

  18. Interaction Patterns and Facilitation of Peer Learning.

    ERIC Educational Resources Information Center

    Shaw, Marvin E.; And Others

    1979-01-01

    Data show that giving information to members of a group is more important in determining the perception by others that the person is facilitating group performance. Asking for information and opinions is more important in actual facilitation of group learning. Social-emotional support becomes important after initial phases of group interaction.…

  19. Interparticle migration of metal cations in stream sediments as a factor in toxics transport

    USGS Publications Warehouse

    Jackman, A.P.; Kennedy, V.C.; Bhatia, N.

    2001-01-01

    Sorption of metal cations by stream sediments is an important process affecting the movement of released contaminants in the environment. The ability of cations to desorb from one sediment particle and subsequently sorb to another can greatly affect metal transport rates but rates for this process have not been reported. The objective of this study was to determine the rate at which sorbed metals can migrate from contaminated sediment particles to uncontaminated sediment particles as a function of the concentration of the contaminating solution and the duration of the contact with the contaminating solution. Samples of small sediment particles were exposed to solutions containing cobalt, after which they were rinsed and combined with larger uncontaminated sediment particles in the presence of stream water. Initial concentrations of the contaminating solution ranged from 1ng/l to 1000mg/l and exposures to the contaminating solution ranged from 6h to 14 days. The rate of the migration increased with increasing concentrations in the contaminating solution and with decreasing times of exposure to the contaminating solution. Under the conditions of these experiments, the time required for the migration to reach equilibrium was on the order of months or longer. In separate experiments, the kinetics of adsorption and desorption of cobalt were measured as a function of concentration of the contaminating solution. The time required to reach adsorption equilibrium increased with increasing concentration in the contaminating solution. Times to sorption equilibrium were on the order of months. Desorption was much slower than adsorption and, together with intraparticle diffusion, probably controls the rate of migration from contaminated to uncontaminated sediment. The results of this study show that interparticle migration of metal cations can proceed at significant rates that are strongly influenced by the length of time that the metal has been in contact with the sediment

  20. In vivo application of chitosan to facilitate intestinal acyclovir absorption in rats.

    PubMed

    Masuda, Ayumi; Goto, Yuko; Kurosaki, Yuji; Aiba, Tetsuya

    2012-07-01

    The effect of chitosan on the intestinal absorption of acyclovir (ACV) was evaluated in rats, and factors influencing its facilitative effect on the ACV absorption were examined. When ACV solution containing 1% chitosan with an average molecular weight of 150 kDa was administered into the upper jejunum, a significant increase in the plasma ACV concentration was observed, with the peak ACV concentration being eight times greater than that observed with the chitosan-free solution. The chitosan-free ACV solution, whose viscosity was adjusted to remain unchanged with polyethylene glycol, did not cause an increase in the plasma concentration, and neither did the chitosan-free solutions substitutionally containing low molecular cationic compounds, triethanolamine and kanamycin. When chitosan was digested with chitosanase to shorten its polycationic polysaccharide structure, chitosan subjected to 150-min digestion retained its facilitative effect on ACV absorption, but that subjected to 420-min digestion no longer caused facilitation, in which its average molecular weight was reduced to around 10 kDa. It is therefore indicated that intestinal ACV absorption can be facilitated with chitosan, and that it is necessary for chitosan to have a certain length of polycationic polysaccharide structure to exert such facilitation.