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Sample records for alkali cations remaining

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

    DOEpatents

    Jackovitz, John F.; Pantier, Earl A.

    1982-05-18

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

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

    PubMed

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

    2016-08-21

    The alkali metal ion affinity of guanine quadruplexes has been studied using dispersion-corrected density functional theory (DFT-D). We have done computational investigations in aqueous solution that mimics artificial supramolecular conditions where guanine bases assemble into stacked quartets as well as biological environments in which telomeric quadruplexes are formed. In both cases, an alkali metal cation is needed to assist self-assembly. Our quantum chemical computations on these supramolecular systems are able to reproduce the experimental order of affinity of the guanine quadruplexes for the cations Li(+), Na(+), K(+), Rb(+), and Cs(+). The strongest binding is computed between the potassium cation and the quadruplex as it occurs in nature. The desolvation and the size of alkali metal cations are thought to be responsible for the order of affinity. Until now, the relative importance of these two factors has remained unclear and debated. By assessing the quantum chemical 'size' of the cation, determining the amount of deformation of the quadruplex needed to accommodate the cation and through the energy decomposition analysis (EDA) of the interaction energy between the cation and the guanines, we reveal that the desolvation and size of the alkali metal cation are both almost equally responsible for the order of affinity. PMID:27185388

  3. High and rapid alkali cation storage in ultramicroporous carbonaceous materials

    NASA Astrophysics Data System (ADS)

    Yun, Young Soo; Lee, Seulbee; Kim, Na Rae; Kang, Minjee; Leal, Cecilia; Park, Kyu-Young; Kang, Kisuk; Jin, Hyoung-Joon

    2016-05-01

    To achieve better supercapacitor performance, efforts have focused on increasing the specific surface area of electrode materials to obtain higher energy and power density. The control of pores in these materials is one of the most effective ways to increase the surface area. However, when the size of pores decreases to a sub-nanometer regime, it becomes difficult to apply the conventional parallel-plate capacitor model because the charge separation distance (d-value) of the electrical double layer has a similar length scale. In this study, ultramicroporous carbonaceous materials (UCMs) containing sub-nanometer-scale pores are fabricated using a simple in situ carbonization/activation of cellulose-based compounds containing potassium. The results show that alkali cations act as charge carriers in the ultramicropores (<0.7 nm), and these materials can deliver high capacitances of ∼300 F g-1 at 0.5 A g-1 and 130 F g-1, even at a high current rate of 65 A g-1 in an aqueous medium. In addition, the UCM-based symmetric supercapacitors are stable over 10,000 cycles and have a high energy and power densities of 8.4 Wh kg-1 and 15,000 W kg-1, respectively. This study provides a better understanding of the effects of ultramicropores in alkali cation storage.

  4. Control of the alkali cation alignment in Prussian blue framework.

    PubMed

    Matsuda, Tomoyuki; Kim, Jungeun; Moritomo, Yutaka

    2012-07-01

    We found that the alignments of the alkali cations can be controlled by a distortion of Prussian blue framework; the rubidium ions form a rod structure in a distorted framework of Rb(0.85)Cu[Fe(CN)(6)](0.95)·1.3H(2)O, while the cesium ions are isolated dot structures in a non-distorted framework of Cs(0.97)Cu[Fe(CN)(6)](0.99)·1.1H(2)O. The Madelung energy calculations revealed that the novel rod structure is stabilized by the alternating rotations of the [Fe(CN)(6)] units within the three-dimensional coordination polymer framework. PMID:22466815

  5. 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

  6. 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

  7. Coordination Chemistry of Alkali and Alkaline-Earth Cations with Macrocyclic Ligands.

    ERIC Educational Resources Information Center

    Dietrich, Bernard

    1985-01-01

    Discusses: (l) alkali and alkaline-earth cations in biology (considering naturally occurring lonophores, their X-ray structures, and physiochemical studies); (2) synthetic complexing agents for groups IA and IIA; and (3) ion transport across membranes (examining neutral macrobicyclic ligands as metal cation carriers, transport by anionic carriers,…

  8. 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.

  9. Enhancing electrocatalytic hydrogen evolution by nickel salicylaldimine complexes with alkali metal cations in aqueous media.

    PubMed

    Shao, Haiyan; Muduli, Subas K; Tran, Phong D; Soo, Han Sen

    2016-02-18

    New salicylaldimine nickel complexes, comprising only earth-abundant elements, have been developed for electrocatalytic hydrogen evolution in aqueous media. The second-sphere ether functionalities on the periphery of the complexes enhance the electrocatalytic activity in the presence of alkali metal cations. The electrocatalysts demonstrate improved performances especially in the economical and sustainable seawater reaction medium. PMID:26779580

  10. Theoretical study of alpha/beta-alanine and their protonated/alkali metal cationized complexes.

    PubMed

    Abirami, S; Xing, Y M; Tsang, C W; Ma, N L

    2005-01-27

    Density functional theory has been employed to model the structure and the relative stabilities of alpha/beta-alanine conformers and their protonated and alkali metal cationized complexes. In general, we find that the behavior of the beta-alanine (beta-Ala) system is quite similar to that of alpha-alanine (alpha-Ala). However, the presence of the methylene group (-CH2-) at the beta position in beta-Ala leads to a few key differences. First, the intramolecular hydrogen bonding patterns are different between free alpha- and beta-Ala. Second, the stability of zwitterionic species (in either the free ligand or alkali metal cationized complexes) is often enhanced in beta-Ala. Third, the preferred mode of alkali metal cation (M+) binding may also differ in alpha- and beta-Ala. Natural energy decomposition analysis has been applied here to gain further insight into the effects of the ligand, cation size, and mode of binding on the nature of interaction in these M+-Ala complexes. PMID:16833371

  11. Ultrafine Na-4-mica: uptake of alkali and alkaline earth metal cations by ion exchange.

    PubMed

    Kodama, Tatsuya; Ueda, Masahito; Nakamuro, Yumiko; Shimizu, Ken-ichi; Komarneni, Sridhar

    2004-06-01

    The cation exchange properties of alkali and alkaline earth metal cations at room temperature were investigated on an ultrafine, highly charged Na-4-mica (with the ideal mica composition Na4Mg6Al4Si4O20F4.xH2O). Ultrafine mica crystallites of 200 nm in size led to faster Sr2+ uptake kinetics in comparison to larger mica crystallites. The alkali metal ion (K+, Cs+, and Li+) exchange uptake was rapid, and complete exchange occurred within 30 min. For the alkaline earth metal ions Ba2+, Ca2+, and Mg2+, however, the exchange uptake required lengthy periods from 3 days to 4 weeks to be completed, similar to its Sr uptake, as previously reported. Kinetic models of the modified Freundlich and parabolic diffusion were examined for the experimental data on the Ba2+, Ca2+, and Mg2+ uptakes. The modified Freundlich model described well the Ba2+ ion uptake kinetics as well as that for the Sr2+ ion, while for the Ca2+ and Mg2+ ions the parabolic diffusion model showed better fitting. The alkali and alkaline earth ion exchange isotherms were also determined in comparison to the Sr2+ exchange isotherm. The thermodynamic equilibria for these cations were compared by using Kielland plots evaluated from the isotherms. PMID:15984251

  12. Local reactivity descriptors to predict the strength of Lewis acid sites in alkali cation-exchanged zeolites

    NASA Astrophysics Data System (ADS)

    Deka, Ramesh Ch.; Kinkar Roy, Ram; Hirao, Kimihiko

    2004-05-01

    Lewis acidity of alkali cation-exchanged zeolite is studied using local reactivity descriptors based on hard-soft acid-base (HSAB) concept. The local softness for nucleophilic attack ( sx+), local softness for electrophilic attack ( sx-) and their ratio, which is called `relative electrophilicity' ( sx+/ sx-), are calculated for the exchanged cations and Lewis acidity of the cations is found to decrease in the order: Li + > Na + > K + > Rb + > Cs +. Calculated blue shift of CO vibrational frequency (Δ ν) and interaction energy of CO molecule with alkali cation-exchanged zeolite clusters vary linearly with sx+/ sx- values.

  13. 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

  14. [Oat growth and cation absorption characteristics under salt and alkali stress].

    PubMed

    Fan, Yuan; Ren, Chang-Zhong; Li, Pin-Fang; Ren, Tu-Sheng

    2011-11-01

    This paper monitored the oat growth and cation absorption characteristics on a saline-alkali soil in the Baicheng region of Jilin Province under low, medium, and high levels of salt stress. No significant differences were observed in the shoot growth and yield components under the three levels of salt stress, but the root biomass and root/shoot ratio decreased significantly with increasing salt stress level. At maturing stage, the root/shoot ratio under medium and high salt stresses was 77.2% and 64.5% of that under low salt stress, respectively. Under the three levels of salt stress, the K+/Na+ and Ca2+/Na+ ratios in oat plant had significant differences at trefoil stage, but no significant differences at heading stage. With the increase of salt stress level, the cation absorption selectivity coefficient of oat at filling stage decreased significantly, but the transportation selectivity coefficient had no significant difference under the three levels of stress. It was concluded that oat could adapt to the salt and alkali stress of soda-alkaline soil to some extent, and the adaptation capability decreased with the increasing level of stress. The decrease of oat root biomass and the stronger ion selective absorption capacity at heading stage under salt and alkali stress could benefit the shoot growth and yield components of oat. PMID:22303664

  15. Gas-phase synthesis of hydrodiphenylcyclopropenylium via nonclassical Favorskii rearrangement from alkali-cationized alpha,alpha'-dibromodibenzyl ketone.

    PubMed

    Zhao, Zhi-Xiong; Wang, Hao-Yang; Xu, Chu; Guo, Yin-Long

    2010-09-15

    The gas-phase synthesis of hydrodiphenylcyclopropenylium from alkali-cationized alpha,alpha'-dibromodibenzyl ketone (1) via nonclassical Lewis-acid-induced Favorskii rearrangement has been studied by electrospray ionization/tandem mass spectrometry (ESI-MS/MS) and theoretical methods, showing that cations [1-Br](+) by debromination from 1 and 1.M(+)(M = Li or Na) by alkali-metal cationization of 1 could convert into the protonated diphenylcyclopropenone 2.H(+) by collision-induced dissociation in the gas phase. A concerted mechanism for the Lewis-acid-induced Favorskii rearrangement from alkali-metal-cationized alpha,alpha'-dibromodibenzyl ketone was proposed and studied, based on mass spectrometric results and theoretical methods. PMID:20740544

  16. Capillary electrophoresis of alkali and alkaline-earth cations with imidazole or benzylamine buffers

    SciTech Connect

    Morin, P.; Francois, C.; Dreux, M. . Lab. de Chimie Bioorganique et Analytique)

    1994-01-01

    The separation of alkali, alkaline earth, and ammonium cations in several samples of water was achieved by capillary electrophoresis with indirect UV detection. A solution of imidazole (10[sup [minus]2] M, pH 4.5) was used as a buffer to resolve a mixture of six cations (K[sup +], Na[sup +], Ca[sup 2+], Ba[sup 2+], Li[sup +] and Mg[sup 2+]) by capillary electrophoresis at 214 nm in less than 10 min. The addition of potassium cation to the running buffer has an influence on the resolution of Ca[sup 2+]/Na[sup +] and Na[sup +]/Mg[sup 2+] peaks. A linear relationship between the corrected peak area and concentration was obtained in the 1--10 ppm range for these cations using a hydrodynamic injector. This electrophoretic system permitted the separation of these inorganic cations at a 50 ppb-level concentration with a hydrodynamic injection, thus making it possible to quantitatively determine their presence in mineral waters by capillary electrophoresis. At pH 4.5, potassium and ammonium unfortunately have identical ionic mobilities causing them to comigrate in an imidazole buffer. Using an alkaline solution of benzylamine as carrier electrolyte, their separation can be successfully achieved with excellent resolution at 204 nm. The analyses of tap water and several mineral waters have been achieved by capillary electrophoresis.

  17. Molecular mechanics (MM3) calculations on benzocrown ether complexes of the alkali and alkaline earth cations

    SciTech Connect

    Yang, Linrong R.; Hay, B.P.

    1997-12-31

    The new metal-ligand feature of MM3 has been extended to benzocrown ether complexes of alkali and alkaline earth cations. Over 50 complexes were compared with the crystal structures retrieved from Cambridge Crystal Database. The results agree with experimental data. The averages of absolute deviations between experimental and calculated structural features are: metal-oxygen bond length, 0.03 {angstrom}; Metal-oxygen-carbon angles, 4.1{degrees}; and Metal-oxygen-carbon-carbon angles: 5.1{degrees}. Development of structure-function relationships is in progress.

  18. Photoionization of the alkali dimer cations Li+2, Na+2 and LiNa+

    NASA Astrophysics Data System (ADS)

    Dumitriu, Irina; Vanne, Yulian V.; Awasthi, Manohar; Saenz, Alejandro

    2007-05-01

    Photoionization cross sections for the three alkali dimer cations (Li+2, Na+2 and LiNa+) were calculated at the equilibrium internuclear distance for parallel, perpendicular and isotropic orientations of the molecular axis with respect to the field. A model-potential method was used for the description of the cores. The influence of the model-potential parameters on the photoionization spectra was investigated. Two different methods, a time-independent and a time-dependent one, were implemented and used for computing the cross sections.

  19. Emerging roles of alkali cation/proton exchangers in organellar homeostasis

    PubMed Central

    Orlowski, John; Grinstein, Sergio

    2016-01-01

    The regulated movement of monovalent cations such as H+, Li+, Na+ and K+ across biological membranes influences a myriad of cellular processes and is fundamental to all living organisms. This is accomplished by a multiplicity of ion channels, pumps and transporters. Our insight into their molecular, cellular and physiological diversity has increased greatly in the past few years with the advent of genome sequencing, genetic manipulation and sophisticated imaging techniques. One of the revelations from these studies is the emergence of novel alkali cation/protons exchangers that are present in endomembranes, where they function to regulate not only intraorganellar pH but also vesicular biogenesis, trafficking and other aspects of cellular homeostasis. PMID:17646094

  20. The syntheses of phenol-containing azamacrocycles and liquid membrane transports of alkali cations

    NASA Astrophysics Data System (ADS)

    Ma, Shu-Lan; Qi, Chuan-Min; Zhu, Wen-Xiang; Guo, Qian-Ling; Liu, Ying-Chun; Zhang, Jing

    2005-01-01

    Two new tetra- N-substituted tetraazacrown ether derivatives, 4,7,13,16-tetra(2-hydroxy-3,4-dimethylbenzyl)-1,10-dioxa-4,7,13,16-tetraazacyclooctadecane (1) and 4,7,13,16-tetra(5- t-butyl-2-hydroxybenzyl)-1,10-dioxa-4,7,13,16-tetraazacyclooctadecane (2), have been synthesized via one-pot Mannich reaction. The compound 2 was structurally characterized. The liquid membrane transports of alkali metal cations using these two new macrocycles and the other two bisphenol-containing diaza-18-crown-6 ligands as ion-carriers were also studied. The results show that the rates of cation transport are closely related to the number of nitrogen donors and the steric effect of the substituted groups. Compared with some macrocyclic ligands, the two newly synthesized tetraazamacrocycles showed a good selectivity for Li +, and the two diazamacrocycles showed a good selectivity for Na +.

  1. Study of Ion Specific Interactions of Alkali Cations with Dicarboxylate Dianions

    SciTech Connect

    Murdachaew, Garold; Valiev, Marat; Kathmann, Shawn M.; Wang, Xue B.

    2012-02-10

    Alkali metal cations often show pronounced ion specific interactions and selectivity with macromolecules in biological processes, colloids, and interfacial sciences, but a fundamental understanding about the underlying microscopic mechanism is still very limited. Here we report a direct probe of interactions between alkali metal cations (M{sup +}) and dicarboxylate dianions, O{sub 2}C(CH{sub 2})nCO{sub 2} (D{sub n}{sup 2-}) in the gas phase by combined photoelectron spectroscopy (PES) and ab initio electronic structure calculation on nine M{sup +}-D{sub n}{sup 2-} complexes (M = Li, Na, K; n = 2, 4, 6). PES spectra show that the electron binding energy (EBE) decreases from Li{sup +} to Na{sup +} to K{sup +} for complexes of M{sup +}-D{sub 2}{sup 2-}, whereas the order is Li{sup +} cation M{sup +}. The observed variance of EBEs reflects how well a specific dicarboxylate dianion accommodates each M{sup +}. This work demonstrates the delicate interplay among several factors (electrostatic interaction, size matching, and strain energy) that likely play critical roles in determining the structures and energetics of gaseous clusters as well as ion specificity and selectivity in solutions and biological systems.

  2. Ca(2+) function in photosynthetic oxygen evolution studied by alkali metal cations substitution.

    PubMed

    Ono, T; Rompel, A; Mino, H; Chiba, N

    2001-10-01

    Effects of adding monovalent alkali metal cations to Ca(2+)-depleted photosystem (PS)II membranes on the biochemical and spectroscopic properties of the oxygen-evolving complex were studied. The Ca(2+)-dependent oxygen evolution was competitively inhibited by K(+), Rb(+), and Cs(+), the ionic radii of which are larger than the radius of Ca(2+) but not inhibited significantly by Li(+) and Na(+), the ionic radii of which are smaller than that of Ca(2+). Ca(2+)-depleted membranes without metal cation supplementation showed normal S(2) multiline electron paramagnetic resonance (EPR) signal and an S(2)Q(A)(-) thermoluminescence (TL) band with a normal peak temperature after illumination under conditions for single turnover of PSII. Membranes supplemented with Li(+) or Na(+) showed properties similar to those of the Ca(2+)-depleted membranes, except for a small difference in the TL peak temperatures. The peak temperature of the TL band of membranes supplemented with K(+), Rb(+), or Cs(+) was elevated to approximately 38 degrees C which coincided with that of Y(D)(+)Q(A)(-) TL band, and no S(2) EPR signals were detected. The K(+)-induced high-temperature TL band and the S(2)Q(A)(-) TL band were interconvertible by the addition of K(+) or Ca(2+) in the dark. Both the Ca(2+)-depleted and the K(+)-substituted membranes showed the narrow EPR signal corresponding to the S(2)Y(Z)(+) state at g = 2 by illuminating the membranes under multiple turnover conditions. These results indicate that the ionic radii of the cations occupying Ca(2+)-binding site crucially affect the properties of the manganese cluster. PMID:11566758

  3. Ion specific effects of alkali cations on the catalytic activity of HIV-1 protease.

    PubMed

    Pokorná, Jana; Heyda, Jan; Konvalinka, Jan

    2013-01-01

    Human immunodeficiency virus 1 protease (HIV-1 PR), an important therapeutic target for the treatment of AIDS, is one of the most well-studied enzymes. However, there is still much to learn about the regulation of the activity and inhibition of this key viral enzyme. Specifically, the mechanism of activation of HIV-1 PR from the viral polyprotein upon HIV maturation is still not understood. It has been suggested that external factors like pH or salt concentration might contribute to regulation of this crucial step in the viral life cycle. Recently, we analyzed the activity of HIV-1 PR in aqueous solutions of sodium and potassium chloride by experimental determination of enzyme kinetics and molecular dynamics simulations. We showed that the effect of salt concentration is cation-specific [Heyda et al., Phys. Chem. Chem. Phys., 2009 (11), 7599]. In this study, we extended this analysis for other alkali cations and found that the dependence of the initial velocity of peptide substrate hydrolysis on the nature of the cation follows the Hofmeister series, with the exception of caesium. Significantly higher catalytic efficiencies both in terms of substrate binding (K(M)) and turnover number (kcat) are observed in the presence of K+ compared to Na+ or Li+ at corresponding salt concentrations. Molecular dynamics simulations suggest that both lithium and sodium are attracted more strongly than potassium and caesium to the protein surface, mostly due to stronger interactions with carboxylate side chain groups of aspartates and glutamates. Furthermore, we observed a surprising decrease in the K(M) value for a specific substrate at very low salt concentration. The molecular mechanism of this phenomenon will be further analyzed. PMID:23795510

  4. An extended basis set {ital ab} {ital initio} study of alkali metal cation--water clusters

    SciTech Connect

    Feller, D.; Glendening, E.D.; Woon, D.E.; Feyereisen, M.W.

    1995-09-01

    Ionic clusters comprised of a single alkali metal cation and up to eight water molecules were studied at the Hartree--Fock and correlated levels of theory using the correlation consistent sequence of basis sets. Estimates of the degree of convergence in the computed properties with respect to the complete basis set limit were facilitated by the underlying systematic manner in which the correlation consistent sets approach completeness. In favorable cases, improved property values could be obtained by fitting finite basis set results with a simple analytical expression in order to extrapolate to the complete basis set limit. The sensitivity of structures and binding energies were analyzed with regard to the inclusion of valence and core-valence correlation recovery at the MP2, MP4, and CCSD(T) levels of theory. The replacement of metal core electrons and the introduction of relativistic contributions via effective core potentials was compared to corresponding all-electron results. {copyright} {ital 1995} {ital American} {ital Institute} {ital of} {ital Physics}.

  5. Selective trans-membrane transport of alkali and alkaline earth cations through graphene oxide membranes based on cation-π interactions.

    PubMed

    Sun, Pengzhan; Zheng, Feng; Zhu, Miao; Song, Zhigong; Wang, Kunlin; Zhong, Minlin; Wu, Dehai; Little, Reginald B; Xu, Zhiping; Zhu, Hongwei

    2014-01-28

    Graphene and graphene oxide (G-O) have been demonstrated to be excellent filters for various gases and liquids, showing potential applications in areas such as molecular sieving and water desalination. In this paper, the selective trans-membrane transport properties of alkali and alkaline earth cations through a membrane composed of stacked and overlapped G-O sheets ("G-O membrane") are investigated. The thermodynamics of the ion transport process reveal that the competition between the generated thermal motions and the interactions of cations with the G-O sheets results in the different penetration behaviors to temperature variations for the considered cations (K(+), Mg(2+), Ca(2+), and Ba(2+)). The interactions between the studied metal atoms and graphene are quantified by first-principles calculations based on the plane-wave-basis-set density functional theory (DFT) approach. The mechanism of the selective ion trans-membrane transportation is discussed further and found to be consistent with the concept of cation-π interactions involved in biological systems. The balance between cation-π interactions of the cations considered with the sp(2) clusters of G-O membranes and the desolvation effect of the ions is responsible for the selectivity of G-O membranes toward the penetration of different ions. These results help us better understand the ion transport process through G-O membranes, from which the possibility of modeling the ion transport behavior of cellular membrane using G-O can be discussed further. The selectivity toward different ions also makes G-O membrane a promising candidate in areas of membrane separations. PMID:24401025

  6. Preparation of decarboxylic-functionalized weak cation exchanger and application for simultaneous separation of alkali, alkaline earth and transition metals.

    PubMed

    Peng, Yahui; Gan, Yihui; He, Chengxia; Yang, Bingcheng; Guo, Zhimou; Liang, Xinmiao

    2016-06-01

    A novel weak cation exchanger (WCX) with dicarboxyl groups functionalized has been developed by clicking mercaptosuccinic acid onto silica gel. The simple synthesis starts with modification of silica gel with triethoxyvinylsilane, followed by efficient coupling vinyl-bonded silica with mercaptosuccinic acid via a "thiol-ene" click reaction. The obtained WCX demonstrated good separation and high selectivity towards common metals. Simultaneous separation of 10 alkali, alkaline earth and transition metals was achieved within 12min. Ion exchange and complex mechanism dominates the separation process. Its utility was demonstrated for determination of metals in tap water. PMID:27130093

  7. Structural Role of Alkali Cations in Calcium Aluminosilicate Glasses as Examined Using Oxygen-17 Solid-State Nuclear Magnetic Resonance Spectroscopy

    NASA Astrophysics Data System (ADS)

    Sukenaga, Sohei; Kanehashi, Koji; Shibata, Hiroyuki; Saito, Noritaka; Nakashima, Kunihiko

    2016-05-01

    The structural roles of alkali and calcium cations are important for understanding the physical and chemical properties of aluminosilicate melts and glasses. Recently, oxygen-17 nuclear magnetic resonance (17O NMR) studies of calcium-sodium aluminosilicate glasses showed that these structural roles are not randomly given, but rather each cation has its own preferential role. However, the relationship between cation type and role preference in calcium aluminosilicate glass is not completely understood. In the present study, the structural roles of lithium, sodium, and potassium cations in selected calcium aluminosilicate glasses are investigated using 17O solid-state NMR experiments. Data from these experiments clearly show that potassium cations have a notably stronger tendency to act as charge compensators within the network structure, compared to sodium and lithium cations. The result of 17O NMR experiment also showed that sodium and lithium cations in part act as network modifier alongside with calcium cations.

  8. Structural Role of Alkali Cations in Calcium Aluminosilicate Glasses as Examined Using Oxygen-17 Solid-State Nuclear Magnetic Resonance Spectroscopy

    NASA Astrophysics Data System (ADS)

    Sukenaga, Sohei; Kanehashi, Koji; Shibata, Hiroyuki; Saito, Noritaka; Nakashima, Kunihiko

    2016-08-01

    The structural roles of alkali and calcium cations are important for understanding the physical and chemical properties of aluminosilicate melts and glasses. Recently, oxygen-17 nuclear magnetic resonance (17O NMR) studies of calcium-sodium aluminosilicate glasses showed that these structural roles are not randomly given, but rather each cation has its own preferential role. However, the relationship between cation type and role preference in calcium aluminosilicate glass is not completely understood. In the present study, the structural roles of lithium, sodium, and potassium cations in selected calcium aluminosilicate glasses are investigated using 17O solid-state NMR experiments. Data from these experiments clearly show that potassium cations have a notably stronger tendency to act as charge compensators within the network structure, compared to sodium and lithium cations. The result of 17O NMR experiment also showed that sodium and lithium cations in part act as network modifier alongside with calcium cations.

  9. Competition between pi and non-pi cation-binding sites in aromatic amino acids: a theoretical study of alkali metal cation (Li+, Na+, K+)-phenylalanine complexes.

    PubMed

    Siu, Fung Ming; Ma, Ngai Ling; Tsang, Chun Wai

    2004-04-19

    To understand the cation-pi interaction in aromatic amino acids and peptides, the binding of M(+) (where M(+) = Li(+), Na(+), and K(+)) to phenylalanine (Phe) is studied at the best level of density functional theory reported so far. The different modes of M(+) binding show the same order of binding affinity (Li(+)>Na(+)>K(+)), in the approximate ratio of 2.2:1.5:1.0. The most stable binding mode is one in which the M(+) is stabilized by a tridentate interaction between the cation and the carbonyl oxygen (O[double bond]C), amino nitrogen (--NH(2)), and aromatic pi ring; the absolute Li(+), Na(+), and K(+) affinities are estimated theoretically to be 275, 201, and 141 kJ mol(-1), respectively. Factors affecting the relative stabilities of various M(+)-Phe binding modes and conformers have been identified, with ion-dipole interaction playing an important role. We found that the trend of pi and non-pi cation bonding distances (Na(+)-pi>Na(+)-N>Na(+)-O and K(+)-pi>K(+)-N>K(+)-O) in our theoretical Na(+)/K(+)-Phe structures are in agreement with the reported X-ray crystal structures of model synthetic receptors (sodium and potassium bound lariat ether complexes), even though the average alkali metal cation-pi distance found in the crystal structures is longer. This difference between the solid and the gas-phase structures can be reconciled by taking the higher coordination number of the cations in the lariat ether complexes into account. PMID:15079836

  10. Influence of alkali metal cations on the thermal, mechanical and morphological properties of rectorite/chitosan bio-nanocomposite films.

    PubMed

    Babul Reddy, A; Jayaramudu, J; Siva Mohan Reddy, G; Manjula, B; Sadiku, E R

    2015-05-20

    The main theme of this work is to study the influence of ion-exchangeable alkali metal cations, such as: Li(+), Na(+), K(+), and Cs(+) on the thermal, mechanical and morphological properties. In this regard, a set of rectorite/chitosan (REC-CS) bio-nanocomposite films (BNCFs) was prepared by facile reaction of chitosan with ion-exchanged REC clay. The microstructure and morphology of BNCFs were investigated with XRD, TEM, SEM and AFM. Thermal and tensile properties of BNCFs were also investigated. As revealed from TEM and XRD results, the BNCFs featured a mixed morphology. Some intercalated clay sheets, together with nano-sized clay tactoids were obtained in LiREC/CS, NaREC/CS and KREC/CS of the BNCFs. From fractured surface study, via SEM, it was observed that the dispersion of chitosan polymer attaches to (and covers) the clay platelets. FTIR confirmed strong hydrogen bonds between clay and chitosan polymer. In addition, the thermal stabilities significantly varied when alkali metal cations varied from Li(+) to Cs(+). The BNCFs featured high tensile strengths (up to 84 MPa) and tensile moduli (up to 45 GPa). After evaluating these properties of BNCFs, we came to conclusion that these bio-nano composites can be used for packaging applications. PMID:25817663

  11. Alkali metal cation complexation by 1,3-alternate, mono-ionisable calix[4]arene-benzocrown-6 compounds

    DOE PAGESBeta

    Surowiec, Malgorzata A.; Custelcean, Radu; Surowiec, Kazimierz; Bartsch, Richard A.

    2014-04-23

    Alkali metal cation extraction behavior for two series of 1,3-alternate, mono-ionizable calix[4]arene-benzocrown-6 compounds is examined. In Series 1, the proton-ionizable group is a substituent on the benzo group of the polyether ring that directs it away from the crown ether cavity. In Series 2, the proton-ionizable group is attached to one para position in the calixarene framework, thus positioning it over the crown ether ring. Competitive solvent extraction of alkali metal cations from aqueous solutions into chloroform shows high Cs+ efficiency and selectivity. Single-species extraction pH profiles of Cs+ for Series 1 and 2 ligands with the same proton-ionizable groupmore » are very similar. Thus, association of Cs+ with the calixcrown ring is more important than the the proton-ionizable group’s position in relation to the crown ether cavity. Solid-state structures are presented for two unionized ligands from Series 2, as is a crystal containing two different ionized ligand–Cs+ complexes.« less

  12. Alkali metal cation complexation by 1,3-alternate, mono-ionisable calix[4]arene-benzocrown-6 compounds

    SciTech Connect

    Surowiec, Malgorzata A.; Custelcean, Radu; Surowiec, Kazimierz; Bartsch, Richard A.

    2014-04-23

    Alkali metal cation extraction behavior for two series of 1,3-alternate, mono-ionizable calix[4]arene-benzocrown-6 compounds is examined. In Series 1, the proton-ionizable group is a substituent on the benzo group of the polyether ring that directs it away from the crown ether cavity. In Series 2, the proton-ionizable group is attached to one para position in the calixarene framework, thus positioning it over the crown ether ring. Competitive solvent extraction of alkali metal cations from aqueous solutions into chloroform shows high Cs+ efficiency and selectivity. Single-species extraction pH profiles of Cs+ for Series 1 and 2 ligands with the same proton-ionizable group are very similar. Thus, association of Cs+ with the calixcrown ring is more important than the the proton-ionizable group’s position in relation to the crown ether cavity. Solid-state structures are presented for two unionized ligands from Series 2, as is a crystal containing two different ionized ligand–Cs+ complexes.

  13. Structure and photoabsorption properties of cationic alkali dimers solvated in neon clusters.

    PubMed

    Zanuttini, D; Douady, J; Jacquet, E; Giglio, E; Gervais, B

    2010-11-01

    We present a theoretical investigation of the structure and optical absorption of M(2)(+) alkali dimers (M=Li,Na,K) solvated in Ne(n) clusters for n=1 to a few tens Ne atoms. For all these alkali, the lowest-energy isomers are obtained by aggregation of the first Ne atoms at the extremity of the alkali molecule. This particular geometry, common to other M(2)(+)-rare gas clusters, is intimately related to the shape of the electronic density of the X  (2)Σ(g)(+) ground state of the bare M(2)(+) molecules. The structure of the first solvation shell presents equilateral Ne(3) and capped pentagonal Ne(6) motifs, which are characteristic of pure rare gas clusters. The size and geometry of the complete solvation shell depend on the alkali and were obtained at n=22 with a D(4h) symmetry for Li and at n=27 with a D(5h) symmetry for Na. For K, our study suggests that the closure of the first solvation shell occurs well beyond n=36. We show that the atomic arrangement of these clusters has a profound influence on their optical absorption spectrum. In particular, the XΣ transition from the X  (2)Σ(g)(+) ground state to the first excited (2)Σ(u)(+) state is strongly blueshifted in the Frank-Condon area. PMID:21054047

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

    SciTech Connect

    Christensen, J.J.

    1981-04-15

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

  15. The Debaryomyces hansenii NHA1 gene encodes a plasma membrane alkali-metal-cation antiporter with broad substrate specificity.

    PubMed

    Velkova, Klara; Sychrova, Hana

    2006-03-15

    Debaryomyces hansenii is a yeast species often found in salty environments. Its genome sequence is known completely, but the mechanisms behind its halotolerance are poorly understood. In the D. hansenii genome, there is a gene strongly homologous to the Saccharomyces cerevisiae NHA1 gene (encoding a plasma membrane Na+/H+ antiporter). We isolated this DhNHA1 gene from two D. hansenii strains (CBS 767 and CBS 1793) differing in their osmotolerance. Both DhNHA1 alleles were heterologously expressed in a S. cerevisiae strain lacking its own systems for the efflux of alkali metal cations (BW31a, ena1-4delta nha1delta). D. hansenii Na+/H+ antiporters were localized in the plasma membrane of BW31a cells, their presence increased BW31a tolerance to sodium, potassium, lithium and also rubidium. Measurements of Na+ and K+ efflux from S. cerevisiae cells expressing DhNHA1 alleles show that the D. hansenii antiporters efficiently transported both cations out of cells. The sodium and potassium transport activity of Nha1 antiporters from both D. hansenii strains was almost identical, indicating that plasma membrane antiporter activity is not one of the factors determining the different levels of halotolerance in the two strains. PMID:16303259

  16. Selective removal of alkali metal cations from multiply-charged ions via gas-phase ion/ion reactions using weakly coordinating anions.

    PubMed

    Luongo, Carl A; Bu, Jiexun; Burke, Nicole L; Gilbert, Joshua D; Prentice, Boone M; Cummings, Steven; Reed, Christopher A; McLuckey, Scott A

    2015-03-01

    Selective removal of alkali metal cations from mixed cation multiply-charged peptide ions is demonstrated here using gas-phase ion/ion reactions with a series of weakly coordinating anions (WCAs), including hexafluorophosphate (PF6 (-)), tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BARF), tetrakis(pentafluorophenyl)borate (TPPB), and carborane (CHB11Cl11 (-)). In all cases, a long-lived complex is generated by dication/anion condensation followed by ion activation to compare proton transfer with alkali ion transfer from the peptide to the anion. The carborane anion was the only anion studied to undergo dissociation exclusively through loss of the metallated anion, regardless of the studied metal adduct. All other anions studied yield varying abundances of protonated and metallated peptide depending on the peptide sequence and the metal identity. Density functional theory calculations suggest that for the WCAs studied, metal ion transfer is most strongly favored thermodynamically, which is consistent with the experimental results. The carborane anion is demonstrated to be a robust reagent for the selective removal of alkali metal cations from peptide cations with mixtures of excess protons and metal cations. PMID:25560986

  17. Selective Removal of Alkali Metal Cations from Multiply-Charged Ions via Gas-Phase Ion/Ion Reactions Using Weakly Coordinating Anions

    NASA Astrophysics Data System (ADS)

    Luongo, Carl A.; Bu, Jiexun; Burke, Nicole L.; Gilbert, Joshua D.; Prentice, Boone M.; Cummings, Steven; Reed, Christopher A.; McLuckey, Scott A.

    2015-03-01

    Selective removal of alkali metal cations from mixed cation multiply-charged peptide ions is demonstrated here using gas-phase ion/ion reactions with a series of weakly coordinating anions (WCAs), including hexafluorophosphate (PF6 -), tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BARF), tetrakis(pentafluorophenyl)borate (TPPB), and carborane (CHB11Cl11 -). In all cases, a long-lived complex is generated by dication/anion condensation followed by ion activation to compare proton transfer with alkali ion transfer from the peptide to the anion. The carborane anion was the only anion studied to undergo dissociation exclusively through loss of the metallated anion, regardless of the studied metal adduct. All other anions studied yield varying abundances of protonated and metallated peptide depending on the peptide sequence and the metal identity. Density functional theory calculations suggest that for the WCAs studied, metal ion transfer is most strongly favored thermodynamically, which is consistent with the experimental results. The carborane anion is demonstrated to be a robust reagent for the selective removal of alkali metal cations from peptide cations with mixtures of excess protons and metal cations.

  18. Complexation of Donor-Acceptor Substituted Aza-Crowns with Alkali and Alkaline Earth Metal Cations. Charge Transfer and Recoordination in Excited State.

    PubMed

    Volchkov, Valery V; Gostev, Fedor E; Shelaev, Ivan V; Nadtochenko, Viktor A; Dmitrieva, Svetlana N; Gromov, Sergey P; Alfimov, Mikhail V; Melnikov, Mikhail Ya

    2016-03-01

    Complexation between two aza-15-crown-5 ethers bearing electron donor and acceptor fragments and alkali and alkaline earth perchlorates has been studied using absorption, steady-state fluorescence and femtosecond transient absorption spectroscopy. The spectral-luminescent parameters, the stability and dissociation constants of the complexes were calculated. The intramolecular charge transfer reaction takes place both in the excited state of the crowns and their complexes 1:1; the latter is subjected to photorecoordination resulting in a weakening or a complete disruption of coordination bond between nitrogen atom and metal cation, disposed within a cavity of the crown. The compounds investigated can be viewed as novel optical molecular sensors for alkali and alkaline-earth metal cations. The photoejection of a metal cation into the bulk was not observed. PMID:26670689

  19. Tetrazole-5-carboxylic acid based salts of earth alkali and transition metal cations.

    PubMed

    Hartdegen, Vera; Klapötke, Thomas M; Sproll, Stefan M

    2009-10-01

    The tetrazole-5-carboxylate anion was investigated as ligand for earth alkali metal and transition metal complexes. Therefore, the strontium 4a (*3 H(2)O, *2.75 H(2)O, *2.5 H(2)O), barium 4b (*3 H(2)O), copper 4c (*3.5 H(2)O, *4 H(2)O), manganese 4d (*4 H(2)O, *5 H(2)O), and silver tetrazol-5-carboxylate 4e (*1.56 H(2)O) were synthesized and characterized by vibrational spectroscopy (IR), and the crystal structures of 4a (*2.75 H(2)O, *2.5 H(2)O), 4b*3 H(2)O, 4c*4 H(2)O, and 4d*5 H(2)O were determined using single crystal X-ray diffraction. The thermal stability was investigated by DSC-measurements, and the sensitivity toward impact and friction was determined by BAM-standards. The copper, strontium, and barium tetrazole-5-carboxyate proved to be suitable thermal and physical stable colorants for pyrotechnic compositions. The crystal structure of the tetragonal modification of strontium tetrazole-5-carboxyate possesses channels along the c-axis, leading to a porous material. PMID:19780625

  20. Ion-exchange selectivities of periderm and cuticular membranes toward alkali cations

    SciTech Connect

    Ersoz, M.; Duncan, H.J.

    1994-08-01

    The ion-exchange selectivities of lithium, sodium, potassium, and cesium on isolated potato periderm (Solanum tuberosum) and pear fruit cuticular membranes were investigated; the general order of preference both for cation selectivities and ion-exchange capacities was lithium > sodium > potassium > cesium. The potato periderm and pear fruit cuticular membranes exhibited a behavior typical of ion-exchange resins of the weak acid type. At constant pH 7, the ion-exchange capacities of periderm and cuticular membranes increased with hydrated ionic radius, and also with increasing pH and neutral salt concentration, and decreased with crystal ionic radius. Counterion selectivities also exhibited the same behavior. The ion-exchange properties are discussed in terms of the structure and function of potato periderm and pear fruit cuticular membranes.

  1. Stability constants and thermodynamic data for complexes of 12-crown-4 with alkali metal and alkaline-earth cations in methanol solutions

    SciTech Connect

    Buschmann, H.

    1987-03-01

    The formation of 1:1- and 2:1-complexes of the crown ether 12C4 with mono- and bivalent cations was studied in methanol solutions by calorimetric, potentiometric and conductometric titrations. It is shown that not all donor atoms of the ligand 12C4 take part in complex formation. The accuracy of the three experimental methods are checked by comparing the results for the complexation of alkali ions with crown ether 18C6.

  2. Electroosmosis through α-Hemolysin That Depends on Alkali Cation Type.

    PubMed

    Piguet, Fabien; Discala, Francoise; Breton, Marie-France; Pelta, Juan; Bacri, Laurent; Oukhaled, Abdelghani

    2014-12-18

    We demonstrate experimentally the existence of an electroosmotic flow (EOF) through the wild-type nanopore of α-hemolysin in a large range of applied voltages and salt concentrations for two different salts, LiCl and KCl. EOF controls the entry frequency and residence time of small neutral molecules (β-cyclodextrins, βCD) in the nanopore. The strength of EOF depends on the applied voltage, on the salt concentration, and, interestingly, on the nature of the cations in solution. In particular, EOF is stronger in the presence of LiCl than KCl. We interpret our results with a simple theoretical model that takes into account the pore selectivity and the solvation of ions. A stronger EOF in the presence of LiCl is found to originate essentially in a stronger anionic selectivity of the pore. Our work provides a new and easy way to control EOF in protein nanopores, without resorting to chemical modifications of the pore. PMID:26273988

  3. Ion permeation through single channels activated by acetylcholine in denervated toad sartorius skeletal muscle fibers: effects of alkali cations.

    PubMed

    Quartararo, N; Barry, P H; Gage, P W

    1987-01-01

    The gigaohm seal technique was used to study ion permeation through acetylcholine-activated channels in cell-attached patches of the extrajunctional membrane of chronically denervated, enzyme-treated cells from the sartorius muscle of the toad Bufo marinus. The most frequently occurring channel type (greater than 95% of channel openings), provisionally classified as 'extrajunctional,' had a chord conductance of approximately 25 pS under normal conditions (-70 mV, 11 degrees C, Normal Toad Ringer's). The less frequently observed channel type (less than 5% of channel openings), classified as a 'junctional' type, had a conductance of 35 pS under the same conditions, and a similar null potential. In many patches, a small percentage (usually less than 2%) of openings of the extrajunctional channel displayed a lower conductance state. The shape of the I-V curves obtained for the extrajunctional channel depended on the predominant extracellular cation. For Cs and K, the I-V curves were essentially linear over the voltage range +50 to -150 mV across the patch, suggesting that the potential independent component of the energy profile within the channel was symmetrical. For Li, the I-V curve was very nonlinear, displaying a significant sublinearity at hyperpolarized potentials. Both an electrodiffusion and a symmetrical uniform four-barrier, three-site rate-theory model provided reasonable fits to the data, whereas symmetrical two-barrier, single-site rate-theory models did not. For the alkali cations examined, the relative permeability sequence was PCs greater than PK greater than PNa greater than PLi--a "proportional" selectivity sequence. This was different from the single channel conductance sequence which was found to be gamma K greater than gamma Cs greater than gamma Na greater than gamma Li implying that ions do not move independently through the channel. The relative binding constant sequence for the channel sites was found to be a "polarizability" sequence, i

  4. Three Alkali-Metal-Gold-Gallium Systems. Ternary Tunnel Structures and Some Problems with Poorly Ordered Cations

    SciTech Connect

    Smetana, Volodymyr; Miller, Gordon J.; Corbett, John D.

    2012-06-27

    Six new intermetallic compounds have been characterized in the alkali metal (A = Na, Rb, Cs)–gold–gallium systems. Three isostructural compounds with the general composition A0.55Au2Ga2, two others of AAu3Ga2 (A = Rb, Cs), and the related Na13Au41.2Ga30.3 were synthesized via typical high-temperature reactions and their crystal structures determined by single-crystal X-ray diffraction analysis: Na0.56(9)Au2Ga2 (I, I4/mcm, a = 8.718(1) Å, c = 4.857(1) Å, Z = 4), Rb0.56(1)Au2Ga2 (II, I4/mcm, a = 8.950(1) Å, c = 4.829(1) Å, Z = 4), Cs0.54(2)Au2Ga2 (III, I4/mcm, a = 9.077(1) Å, c = 4.815(1) Å, Z = 4), RbAu3Ga2 (IV, Pnma, a = 13.384(3) Å, b = 5.577(1) Å, c = 7.017(1) Å, Z = 4), CsAu3Ga2 (V, Pnma, a = 13.511(3) Å, b = 5.614(2) Å, c = 7.146(1) Å, Z = 4), Na13Au41.2(1)Ga30.3(1) (VI, P6 mmm, a = 19.550(3) Å, c = 8.990(2) Å, Z = 2). The first three compounds (I–III) are isostructural with tetragonal K0.55Au2Ga2 and likewise contain planar eight-member Au/Ga rings that stack along c to generate tunnels and that contain varying degrees of disordered Na–Cs cations. The cation dispositions are much more clearly and reasonably defined by electron density mapping than through least-squares refinements with conventional anisotropic ellipsoids. Orthorhombic AAu3Ga2 (IV, V) are ordered ternary Rb and Cs derivatives of the SrZn5 type structure, demonstrating structural variability within the AAu3Ga2 family. All attempts to prepare an isotypic “NaAu3Ga2” were not successful, but yielded only a similar composition Na13Au41.2Ga30.3 (NaAu3.17Ga2.33) (VI) in a very different structure with two types of cation sites. Crystal orbital Hamilton population (COHP) analysis obtained from tight-binding electronic structure calculations for idealized I–IV via linear muffin-tin-orbital (LMTO) methods emphasized the major contributions of heteroatomic Au–Ga bonding to the structural stability of these compounds. The relative minima (pseudogaps) in the DOS curves for IV

  5. Different Cation Arrangements in Au-In Networks. Syntheses and Structures of Six Intermetallic Compounds in Alkali-Metal-Au-In Systems

    SciTech Connect

    Bin Li; John D. Corbett

    2007-06-20

    Six robust intermetallic compounds with cations in three different tunnel-like structures have been synthesized in alkali-metal-Au-In systems via high-temperature solid-state methods and characterized by X-ray diffraction: AAu{sub 4}-In{sub 6} [A = K (I), Rb (II), F6m2, Z = 1], K{sub 1.76(6)}Au{sub 6}Ln{sub 4} (III,; 4/mcm, Z = 4), and A{sub x}Au{sub 2}In{sub 2} [x{approx} 0.7, A = K (IV), Rb (V), Cs (VI), P4{sub 2}/nmc, Z = 8]. The first type is constructed from a single cage unit: an alkali-metal-centered 21-vertex polyhedron A@AugIn12 with 6-9-6 arrangement of planar rings. The others contain uniaxial arrays of tunnels built of differently puckered eight- and four-member Au/In rings. The largely different cation distributions depend on the tunnel constitutions and cation sizes. Tight-binding electronic structure calculations by linear muffin-tin-orbital (LMTO) methods were performed for I and idealized III in order to help understand their chemical bonding. These also reveal large differences in relativistic effects for Au d orbitals, as well as for different Au sites in each structure.

  6. Different Cation Arrangements in Au-In Networks. Syntheses and Structures of Six Intermetallic compounds in Alkali-Metal-Au-In Systems

    SciTech Connect

    Li, Bin; Corbett, John D.

    2007-06-20

    Six robust intermetallic compounds with cations in three different tunnel-like structures have been synthesized in alkali-metal-Au-In systems via high-temperature solid-state methods and characterized by X-ray diffraction: AAu{sub 4}-In{sub 6} [A = K (I), Rb (II), F6m2, Z = 1], K{sub 1.76(6)}Au{sub 6}Ln{sub 4} (III, /4/mcm, Z = 4), and A{sub x}Au{sub 2}In{sub 2} [x {approx} 0.7, A = K (IV), Rb (V), Cs (VI), P4{sub 2}/nmc, Z = 8]. The first type is constructed from a single cage unit: an alkali-metal-centered 21-vertex polyhedron A{at}AugIn{sub 12} with 6-9-6 arrangement of planar rings. The others contain uniaxial arrays of tunnels built of differently puckered eight- and four-member Au/In rings. The largely different cation distributions depend on the tunnel constitutions and cation sizes. Tight-binding electronic structure calculations by linear muffin-tin-orbital (LMTO) methods were performed for I and idealized III in order to help understand their chemical bonding. These also reveal large differences in relativistic effects for Au d orbitals, as well as for different Au sites in each structure.

  7. Ab initio many-electron study for the low-lying states of the alkali hydride cations in the adiabatic representation

    NASA Astrophysics Data System (ADS)

    Yan, Lingling; Qu, Yizhi; Liu, Chunhua; Wang, Jianguo; Buenker, Robert J.

    2012-03-01

    An ab initio multireference single- and double-excitation configuration interaction (CI) study is carried out for the ground and excited electronic states of alkali-hydride cations (LiH+, NaH+, KH+, RbH+, and CsH+). For all alkali-metal atoms, the first inner-shell and valence electrons (nine active electrons, three for Li) are considered explicitly in the ab initio self-consistent-field and CI calculations. The adiabatic potential energy curves, radial and rotational couplings are calculated and presented. Short-range (˜3 a.u.) potential wells produced by the excitation of the inner-shell electrons are found. The depths of the inner potential wells are much greater than those of the outer wells for the CsH+ system. The computed spectroscopic constants for the long-range potential well of the 2 2Σ+ state are very close to the available theoretical and experimental data. The electronic states of alkali-hydrogen cations are also compared with each other, it is found that the positions of the potential wells shift to larger internuclear distances gradually, and the depths of these potential wells become greater with increasing alkali-metal atomic number. The relationships between structures of the radial coupling matrix elements and the avoiding crossings of the potential curves are analyzed. From NaH+ to CsH+, radial coupling matrix elements display more and more complex structures due to the gradual decrease of energy separations for avoided crossings. Finally, the behavior of some rotational couplings is also shown.

  8. Structures of Hydrated Alkali Metal Cations, M+(H2O)nAr (m = Li, Na, K, rb and Cs, n = 3-5), Using Infrared Photodissociation Spectroscopy and Thermodynamic Analysis

    NASA Astrophysics Data System (ADS)

    Ke, Haochen; van der Linde, Christian; Lisy, James M.

    2014-06-01

    Alkali metal cations play vital roles in chemical and biochemical systems. Lithium is widely used in psychiatric treatment of manic states and bipolar disorder; Sodium and potassium are essential elements, having major biological roles as electrolytes, balancing osmotic pressure on body cells and assisting the electroneurographic signal transmission; Rubidium has seen increasing usage as a supplementation for manic depression and depression treatment; Cesium doped compounds are used as essential catalysts in chemical production and organic synthesis. Since hydrated alkali metal cations are ubiquitous and the basic form of the alkali metal cations in chemical and biochemical systems, their structural and thermodynamic properties serve as the foundation for modeling more complex chemical and biochemical processes, such as ion transport and ion size-selectivity of ionophores and protein channels. By combining mass spectrometry and infrared photodissociation spectroscopy, we have characterized the structures and thermodynamic properties of the hydrated alkali metal cations, i.e. M+(H2O)nAr, (M = Li, Na, K, Rb and Cs, n = 3-5). Ab initio calculations and RRKM-EE (evaporative ensemble) calculations were used to assist in the spectral assignments and thermodynamic analysis. Results showed that the structures of hydrated alkali metal cations were determined predominantly by the competition between non-covalent interactions, i.e. the water---water hydrogen bonding interactions and the water---cation electrostatic interactions. This balance, however, is very delicate and small changes, i.e. different cations, different levels of hydration and different effective temperatures clearly impact the balance.

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

    PubMed

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

    2010-10-26

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

  10. Bonding and singlet-triplet gap of silicon trimer: effects of protonation and attachment of alkali metal cations.

    PubMed

    Tam, Nguyen Minh; Hang, Tran Dieu; Pham, Hung Tan; Nguyen, Huyen Thi; Pham-Ho, My Phuong; Denis, Pablo A; Nguyen, Minh Tho

    2015-04-30

    We revisit the singlet-triplet energy gap (ΔE(ST)) of silicon trimer and evaluate the gaps of its derivatives by attachment of a cation (H(+), Li(+), Na(+), and K(+)) using the wavefunction-based methods including the composite G4, coupled-cluster theory CCSD(T)/CBS, CCSDT and CCSDTQ, and CASSCF/CASPT2 (for Si3) computations. Both (1)A1 and (3)A2' states of Si3 are determined to be degenerate. An intersystem crossing between both states appears to be possible at a point having an apex bond angle of around α = 68 ± 2° which is 16 ± 4 kJ/mol above the ground state. The proton, Li(+) and Na(+) cations tend to favor the low-spin state, whereas the K(+) cation favors the high-spin state. However, they do not modify significantly the ΔE(ST). The proton affinity of silicon trimer is determined as PA(Si3) = 830 ± 4 kJ/mol at 298 K. The metal cation affinities are also predicted to be LiCA(Si3) = 108 ± 8 kJ/mol, NaCA(Si3) = 79 ± 8 kJ/mol and KCA(Si3) = 44 ± 8 kJ/mol. The chemical bonding is probed using the electron localization function, and ring current analyses show that the singlet three-membered ring Si3 is, at most, nonaromatic. Attachment of the proton and Li(+) cation renders it anti-aromatic. PMID:25694392

  11. Specific interactions between alkali metal cations and the KcsA channel studied using ATR-FTIR spectroscopy

    PubMed Central

    Furutani, Yuji; Shimizu, Hirofumi; Asai, Yusuke; Oiki, Shigetoshi; Kandori, Hideki

    2015-01-01

    The X-ray structure of KcsA, a eubacterial potassium channel, displays a selectivity filter composed of four parallel peptide strands. The backbone carbonyl oxygen atoms of these strands solvate multiple K+ ions. KcsA structures show different distributions of ions within the selectivity filter in solutions containing different cations. To assess the interactions of cations with the selectivity filter, we used attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectroscopy. Ion-exchange-induced ATR-FTIR difference spectra were obtained by subtracting the spectrum of KcsA soaked in K+ solution from that obtained in Li+, Na+, Rb+, and Cs+ solutions. Large spectral changes in the amide-I and -II regions were observed upon replacing K+ with smaller-sized cations Li+ and Na+ but not with larger-sized cations Rb+ and Cs+. These results strongly suggest that the selectivity filter carbonyls coordinating Rb+ or Cs+ adopt a conformation similar to those coordinating K+ (cage configuration), but those coordinating Li+ or Na+ adopt a conformation (plane configuration) considerably different from those coordinating K+. We have identified a cation-type sensitive amide-I band at 1681 cm−1 and an insensitive amide-I band at 1659 cm−1. The bands at 1650, 1639, and 1627 cm−1 observed for Na+-coordinating carbonyls were almost identical to those observed in Li+ solution, suggesting that KcsA forms a similar filter structure in Li+ and Na+ solutions. Thus, we conclude that the filter structure adopts a collapsed conformation in Li+ solution that is similar to that in Na+ solution but is in clear contrast to the X-ray crystal structure of KcsA with Li+. PMID:27493853

  12. Characterization of selective binding of alkali cations with carboxylate by x-ray absorption spectroscopy of liquid microjets

    SciTech Connect

    Saykally, Richard J; Uejio, Janel S.; Schwartz, Craig P.; Duffin, Andrew M.; Drisdell, Walter S.; Cohen, Ronald C.; Saykally, Richard J.

    2008-01-08

    We describe an approach for characterizing selective binding between oppositely charged ionic functional groups under biologically relevant conditions. Relative shifts in K-shell x-ray absorption spectra of aqueous cations and carboxylate anions indicate the corresponding binding strengths via perturbations of carbonyl antibonding orbitals. XAS spectra measured for aqueous formate and acetate solutions containing lithium, sodium, and potassium cations reveal monotonically stronger binding of the lighter metals, supporting recent results from simulations and other experiments. The carbon K-edge spectra of the acetate carbonyl feature centered near 290 eV clearly indicate a preferential interaction of sodium versus potassium, which was less apparent with formate. These results are in accord with the Law of Matching Water Affinities, relating relative hydration strengths of ions to their respective tendencies to form contact ion pairs. Density functional theory calculations of K-shell spectra support the experimental findings.

  13. Hydration thermodynamics of the SWy-1 montmorillonite saturated with alkali and alkaline-earth cations: A predictive model

    NASA Astrophysics Data System (ADS)

    Vieillard, Philippe; Blanc, Philippe; Fialips, Claire I.; Gailhanou, Hélène; Gaboreau, Stéphane

    2011-10-01

    The aim of the present work was to study the thermodynamic equilibria between water and a homo-ionic montmorillonite SWy-1 saturated by different cations. The choice of this smectite is justified by the large set of experimental data available from the literature for eight different interlayer cations: Na +, K +, Rb +, Cs +, Mg 2+, Ca 2+, Sr 2+, and Ba 2+. In particular, studies by Cases et al. (1992, 1997) and Bérend et al. (1995) are providing heat of adsorption data, pairs of desorption-adsorption isotherms, and information about the partition of adsorption-desorption water molecules between external surfaces and internal spaces. By calculating the effective amount of hydration water as the difference between the so-called gravimetric water and the surface covering water, a thermodynamic model was then developed, based on the concept of Ransom and Helgeson (1994) considering an asymmetric subregular binary solid solution between a fully hydrated and a anhydrous smectite. A set of six thermodynamic parameters ( ΔH∘hyd,S∘hyd and four Margules parameters) was extracted by a least square method from measurements of enthalpies of adsorption and paired adsorption-desorption isotherms for each interlayer cation. These six initial parameters were then used to determine a complete set of standard thermodynamic hydration parameters ( ΔH∘hyd,ΔG∘hyd,ΔS∘hyd, heat capacity, molar volume, and number of interlayer H 2O) and quantify, for each cation, the number of moles of hydration water molecules as a function of relative humidity and temperature. The validation of the standard state thermodynamic properties of hydration for each end member was carried out using three approaches: (1) a comparison with experimental isotherms obtained on hetero-ionic and homo-ionic SWy-1 smectite at different temperatures; (2) a comparison with the experimental integral enthalpy and entropy of hydration of the SWy-1 smectite; and (3) a comparison with experimental isotherms

  14. A multinuclear solid-state NMR study of alkali metal ions in tetraphenylborate salts, M[BPh4] (M = Na, K, Rb and Cs): what is the NMR signature of cation-pi interactions?

    PubMed

    Wu, Gang; Terskikh, Victor

    2008-10-16

    We report a multinuclear solid-state ( (23)Na, (39)K, (87)Rb, (133)Cs) NMR study of tetraphenylborate salts, M[BPh 4] (M = Na, K, Rb, Cs). These compounds are isostructural in the solid state with the alkali metal ion surrounded by four phenyl groups resulting in strong cation-pi interactions. From analyses of solid-state NMR spectra obtained under stationary and magic-angle spinning (MAS) conditions at 11.75 and 21.15 T, we have obtained the quadrupole coupling constants, C Q, and the chemical shift tensor parameters for the alkali metal ions in these compounds. We found that the observed quadrupole coupling constant for M (+) in M[BPh 4] is determined by a combination of nuclear quadrupole moment, Sternheimer antishielding factor, and unit cell dimensions. On the basis of a comparison between computed paramagnetic and diamagnetic contributions to the total chemical shielding values for commonly found cation-ligand interactions, we conclude that cation-pi interactions give rise to significantly lower paramagnetic shielding contributions than other cation-ligand interactions. As a result, highly negative chemical shifts are expected to be the NMR signature for cations interacting exclusively with pi systems. PMID:18816043

  15. Separation of alkali, alkaline earth and rare earth cations by liquid membranes containing macrocyclic carriers. Fourth progress report, 1 November 1981-31 July 1982

    SciTech Connect

    Christensen, J J; Izatt, R M

    1982-07-31

    The H/sub 2/O-CHCl/sub 3/-H/sub 2/O liquid membrane system was characterized with respect to the effect on cation (K/sup +/) transport rate of salt concentration and anion type. A bulk liquid membrane cell was used. A mathematical model for cation flux is being developed for several cations, several macrocycles, and mixtures of two or three cations. Eu/sup 3 +/ was not transported by 18-crown-6, but its reduced from Eu/sup 2 +/ was. Cation transport properties of calixarenes are also being investigated. Emulsion membrane systems were studied as a way of increasing the cation transport. Pb/sup 2 +/ was found to be transported by dicyclohexano-18-crown-6 through the liquid membrane. Transport rates of metal cation nitrates were measured in a water-toluene-water emulsion membrane system. 14 figures, 7 tables. (DLC)

  16. X-ray, spectroscopic and semiempirical investigation of the structure of lasalocid 6-bromohexyl ester and its complexes with alkali metal cations

    NASA Astrophysics Data System (ADS)

    Huczyński, Adam; Ratajczak-Sitarz, Małgorzata; Katrusiak, Andrzej; Brzezinski, Bogumil

    2011-07-01

    The ionophoric antibiotic lasalocid acid has been converted to a novel 6-bromohexyl ester (LASBR) and its structure has been determined in the crystal by X-ray diffraction and in solution by NMR and FT-IR methods. In the crystal two symmetry-independent LASBR molecules are present. The structure of LASBR in solution is slightly different because the strongest intramolecular C(1) dbnd O⋯H sbnd (3)O hydrogen bond in the pseudo-aromatic ring becomes partially broken and a new hydrogen bond between O(4)H and carbonyl group C(13) dbnd O is formed. LASBR forms complexes with Li +, Na + and K + cations of exclusively 1:1 stoichiometry. The structures of complexes have been studied and visualized using semi-empirical calculation based on results of spectrometric and spectroscopic investigation. It is demonstrated that in contrast to lasalocid acid the novel ester forms preferential complexes with Li + cation.

  17. Intrinsic affinities of alkali cations for 15-crown-5 and 18-crown-6: Bond dissociation energies of gas-phase M{sup +}-crown ether complexes

    SciTech Connect

    More, M.B.; Ray, D.; Armentrout, P.B.

    1999-01-20

    Bond dissociation energies (BDEs) of M{sup +}[c-(C{sub 2}H{sub 4}O){sub 5}] and M{sup +}[c-(C{sub 2}H{sub 4}O){sub 6}] for M = Na, K, Rb, and Cs are reported. The BDEs are determined experimentally by analysis of the thresholds for collision-induced dissociation of the cation-crown ether complexes by xenon measured by using guided ion beam mass spectrometry. In all cases, the primary and lowest energy dissociation channel observed experimentally in endothermic loss of the ligand molecule. The cross section thresholds are interpreted to yield 0 and 298 K BDEs after accounting for the effects of multiple ion-molecule collisions, internal energy of the complexes, and unimolecular decay rates. For both 18-crown-6 and 15-crown-5, the BDEs decrease monotonically with increasing cation size. These results indicate that the intrinsic affinity of c-(C{sub 2}H{sub 4}O){sub 5} and c-(C{sub 2}H{sub 4}O){sub 6} for M{sup +} is determined principally by the charge density of the cation not by the ratio of the ionic radius to the cavity size. The BDEs reported here are in fair agreement with recent ab initio calculations at the MP2 level with 6-31+G* basis sets. The experimental values are systematically smaller than the computed values by 8 {+-} 2 kJ/mol per metal-oxygen interaction. The existence of less strongly bound isomers in the experimental apparatus for Rb{sup +}(15-crown-5) and Cs{sup +}(15-crown-5) appears likely, but their absence for Na{sup +} and K{sup +} complexes indicates interesting metal-dependent dynamics to the formation of such isomers.

  18. Ground-state properties of alkali dimers and their cations (including the elements Li, Na, and K) from ab initio calculations with effective core polarization potentials

    NASA Astrophysics Data System (ADS)

    Müller, Wolfgang; Meyer, Wilfried

    1984-04-01

    Extensive all-electron SCF and valence CI calculations are presented for alkali dimer systems with consideration of intershell correlation effects by use of an effective core polarization potential (CPP), which contains only a single adjustable atomic parameter. High accuracy is obtained for the ground-state spectroscopic constants of the studied molecules. The maximum deviations from accurate experimental data are as follows: 1% or 0.03 Å for Re, 2% or 100 cm-1 for De, 0.5% or 1 cm-1 for ωe, and 0.2% or 100 cm-1 for ionization energies. For experimentally uncertain or unknown values reliable predictions can thus be made. The calculated dipole moments for LiK and NaK agree with experiment to within 0.1%, but for LiNa we obtain a deviation of 8% or 0.036 D. An analysis of molecular core polarization contributions reveals the reasons for some systematic defects in previous pseudopotential calculations.

  19. Salts of alkali metal anions and process of preparing same

    DOEpatents

    Dye, James L.; Ceraso, Joseph M.; Tehan, Frederick J.; Lok, Mei Tak

    1978-01-01

    Compounds of alkali metal anion salts of alkali metal cations in bicyclic polyoxadiamines are disclosed. The salts are prepared by contacting an excess of alkali metal with an alkali metal dissolving solution consisting of a bicyclic polyoxadiamine in a suitable solvent, and recovered by precipitation. The salts have a gold-color crystalline appearance and are stable in a vacuum at -10.degree. C. and below.

  20. Dynamic chiral-at-metal stability of tetrakis(d/l-hfc)Ln(III) complexes capped with an alkali metal cation in solution.

    PubMed

    Lin, Yiji; Zou, Fang; Wan, Shigang; Ouyang, Jie; Lin, Lirong; Zhang, Hui

    2012-06-14

    Chiral tetrakis(β-diketonate) Ln(III) complexes Δ-[NaLa(d-hfc)(4)(CH(3)CN)] (1) and Λ-[NaLa(l-hfc)(4) (CH(3)CN)] (2) (d/l-hfc(-) = 3-heptafluo-robutylryl-(+)/(-)-camphorate) are a pair of enantiomers and crystallize in the same Sohncke space group (P2(1)2(1)2(1)) with dodecahedral (DD) geometry. Typically positive and negative exciton splitting patterns around 320 nm were observed in the solid-state circular dichroism (CD) spectra of complexes 1 and 2, which indicate that their shell configurational chiralities are Δ and Λ, respectively. The apparent bisignate couplets in the solid-state CD spectra of [CsLn(d-hfc)(4)(H(2)O)] [Ln = La (3), Yb (5)] and [CsLn(l-hfc)(4)(H(2)O)] [Ln = La (4), Yb (6)] show that they are a pair of enantiomers and their absolute configurations are denoted Δ and Λ, respectively. The crystallographic data of 5 reveals that its coordination polyhedron is the square antiprism (SAP) geometry and it undergoes a phase transition from triclinic (α phase, P1) to monoclinic (β phase, C2) upon cooling. The difference between the two phases is brought about by the temperature dependent behaviour of the coordination water molecules, but this did not affect the configurational chirality of the Δ-SAP-[Yb(d-hfc)(4)](-) moiety. Furthermore, time-dependent CD, UV-vis and (19)F NMR were applied to study the solution behavior of these complexes. It was found that the chiral-at-metal stability of the three pairs of complexes is different and affected by both the Ln(3+) and M(+) ion size. The results show that the Cs(+) cation can retain the metal center chirality and stablize the structures of [Ln(d/l-hfc)(4)](-) or the dissociated tris(d/l-hfc)Ln(III) species in solution for a longer time than that of the Na(+) cation, and it is important that the Cs(+) ion successfully lock the configurational chirality around the Yb(3+) center of the complex species in solution. This is reasoned by the short Cs(+)···FC, Cs(+)···O-Yb and Cs(+)···Yb(3

  1. Effect of alkali cations on two-dimensional networks of two new quaternary thioarsenates (III) prepared by a facile surfactant-thermal method

    NASA Astrophysics Data System (ADS)

    Yan, Dongming; Hou, Peipei; Liu, Chang; Chai, Wenxiang; Zheng, Xuerong; Zhang, Luodong; Zhi, Mingjia; Zhou, Chunmei; Liu, Yi

    2016-09-01

    Two new quaternary thioarsenates(III) NaAg2AsS3·H2O (1) and KAg2AsS3 (2) with high yields have been successfully prepared through a facile surfactant-thermal method. It is interesting that 2 can only be obtained with the aid of ethanediamine (en), which indicates that weak basicity of solvent is beneficial to the growth of 2 compared with 1. Both 1 and 2 feature the similar two-dimensional (2D) layer structures. However, the distortion of the primary honeycomb-like nets in 2 is more severe than that of 1, which demonstrates that Na+ and K+ cations have different structure directing effects on these two thioarsenates(III). Both experimental and theoretical studies confirm 1 and 2 are semiconductors with band gaps in the visible region. Our success in preparing these two quaternary thioarsenates(III) proves that surfactant-thermal technique is a powerful yet facile synthetic method to explore new complex chalcogenides.

  2. Design and synthesis of redox-switched lariat ethers and their application for transport of alkali and alkaline-Earth metal cations across supported liquid membrane.

    PubMed

    Awasthy, Anubhuti; Bhatnagar, Mamta; Tomar, Jyoti; Sharma, Uma

    2006-01-01

    A new class of redox-switched anthraquinone derived lariat ethers 1-(1-anthraquinonyloxy) 3, 6, 9 trioxaundecane 11-ol (M(1)), 1-(1-anthraquinonyloxy) 3, 6 dioxaoctane 9-ol (M(2)), 1-(1-anthraquinonyloxy) 3 oxapentane 5-ol (M(3)), 1-(1-anthraquinonyloxy) 3 oxapentane 5-butane (M(4)), 1-(1-anthraquinonyloxy) 3, 6 dioxaoctane 9-methane (M(5)) and 1-(1-anthraquinonyloxy) 3 oxapentane 5-methane (M(6)) have been synthesized and characterized by spectral analysis. These ionophores were used in liquid membrane carrier facilitated transport of main group metal cations across supported liquid membrane (SLM). Cellulose nitrate membrane was used as membrane support. Effect of various parameters such as variation in concentration of metal as well as ionophore, effect of chain length and end group of ionophore have been studied. The sequence of metal ions transported by ionophore M(1) is Na(+) > Li(+) > K(+) > Ca(2+) > Mg(2+) and the order of metal ions transported by ionophores (M(2)-M(6)) is Li(+) > Na(+) > K(+) > Ca(2+) > Mg(2+). Ionophore M(1) is selective for Na(+), Li(+), and K(+) and ionophores (M(2)-M(6)) are selective for Li(+) and Na(+). PMID:17497021

  3. Alkali Bee

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The alkali bee, Nomia melanderi, is native to deserts and semi-arid desert basins of the western United States. It is a very effective and manageable pollinator for the production of seed in alfalfa (=lucerne) and some other crops, such as onion. It is the world’s only intensively managed ground-n...

  4. The alkali metals: 200 years of surprises.

    PubMed

    Dye, James L

    2015-03-13

    Alkali metal compounds have been known since antiquity. In 1807, Sir Humphry Davy surprised everyone by electrolytically preparing (and naming) potassium and sodium metals. In 1808, he noted their interaction with ammonia, which, 100 years later, was attributed to solvated electrons. After 1960, pulse radiolysis of nearly any solvent produced solvated electrons, which became one of the most studied species in chemistry. In 1968, alkali metal solutions in amines and ethers were shown to contain alkali metal anions in addition to solvated electrons. The advent of crown ethers and cryptands as complexants for alkali cations greatly enhanced alkali metal solubilities. This permitted us to prepare a crystalline salt of Na(-) in 1974, followed by 30 other alkalides with Na(-), K(-), Rb(-) and Cs(-) anions. This firmly established the -1 oxidation state of alkali metals. The synthesis of alkalides led to the crystallization of electrides, with trapped electrons as the anions. Electrides have a variety of electronic and magnetic properties, depending on the geometries and connectivities of the trapping sites. In 2009, the final surprise was the experimental demonstration that alkali metals under high pressure lose their metallic character as the electrons are localized in voids between the alkali cations to become high-pressure electrides! PMID:25666067

  5. Adsorption on Alkali Halides.

    NASA Astrophysics Data System (ADS)

    Urzua Duran, Gilberto Antonio

    1995-01-01

    Using a variety of interionic potentials, I have computed the configurations of adsorbed alkali halides monomers on the (001) surface of selected alkali halides crystals. In the majority of cases studied it is found that the monomer adsorbs perpendicular to the surface with the cation sitting nearly on top of the surface anion. In about ten percent of the cases though the monomer adsorbs tilted from the vertical. In these cases the ion that is closer to the surface can be the cation or the anion. The effect of polarization forces is found to be important. In order to discuss the effects of surface retaxation with adsorbates, I have evaluated the surface relaxation of the alkali halide crystals, using a shell model for the interionic forces. It is found that surface relaxation and rumpling are generally small, especially when the van der Waals forces are included. A theory of the effect of substrate vibrations on the binding of an adsorbed atom is developed. At T = 0 the binding energy is D_0-E, where D_0 is the surface well depth (classical binding energy) and E is the quantum correction. For several simple models, it is found that E is surprisingly model-independent. We compare D _0-E with the binding energies to a rigid substrate, D_0-E_{rs}, and to a vibrationally averaged substrate, D _0-E_{va}. We prove that E_{va}>=q E>=q E_ {rs} and that similar relations hold at finite temperature for the free energy of binding. In most cases E_{rs} is better than E_{va} as an approximation to E.

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

    PubMed

    Pillai, Karthik V; Renneckar, Scott

    2009-04-13

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

  7. Alkali metal sources for OLED devices

    NASA Astrophysics Data System (ADS)

    Cattaneo, Lorena; Longoni, Giorgio; Bonucci, Antonio; Tominetti, Stefano

    2005-07-01

    In OLED organic layers electron injection is improved by using alkali metals as cathodes, to lower work function or, as dopants of organic layer at cathode interface. The creation of an alkali metal layer can be accomplished through conventional physical vapor deposition from a heated dispenser. However alkali metals are very reactive and must be handled in inert atmosphere all through the entire process. If a contamination takes place, it reduces the lithium deposition rate and also the lithium total yield in a not controlled way. An innovative alkali metal dispensing technology has been developed to overcome these problems and ensure OLED alkali metal cathode reliability. The alkali Metal dispenser, called Alkamax, will be able to release up to a few grams of alkali metals (in particular Li and Cs) throughout the adoption of a very stable form of the alkali metal. Lithium, for example, can be evaporated "on demand": the evaporation could be stopped and re-activated without losing alkali metal yield because the metal not yet consumed remains in its stable form. A full characterization of dispensing material, dispenser configuration and dispensing process has been carried out in order to optimize the evaporation and deposition dynamics of alkali metals layers. The study has been performed applying also inside developed simulations tools.

  8. Negative electrodes for non-aqueous secondary batteries composed on conjugated polymer and alkali metal alloying or inserting material

    SciTech Connect

    Shacklette, L.W.; Jow, T.R.; Toth, E.; Maxfield, M.

    1987-05-26

    A battery is described comprising: an anode comprising as the anode active materials one or more conjugated backbone polymers and one or more electroactive materials selected from the group consisting of metals which alloy with alkali metals and alkali metal cation inserting materials; an electrolyte comprising an organic solvent and an alkali-metal salt, and a cathode. The alkali-metal cations from the electrolyte are inserted into the anode as a metal alloy or as an inserted ion in the alkali metal cation inserting material during the charging of the battery.

  9. Contributions to the mixed-alkali effect in molecular dynamics simulations of alkali silicate glasses

    NASA Astrophysics Data System (ADS)

    Lammert, Heiko; Heuer, Andreas

    2005-12-01

    The mixed-alkali effect in the cation dynamics in silicate glasses is analyzed via molecular dynamics simulations. Observations suggest a description of the dynamics in terms of stable sites mostly specific to one ionic species. As main contributions to the mixed-alkali slow down longer residence times and an increased probability of correlated backjumps are identified. The slow down is related to the limited accessibility of foreign sites. The mismatch experienced in a foreign site is stronger and more retarding for the larger ions, the smaller ions can be temporarily accommodated. Also correlations between unlike as well as like cations are demonstrated that support cooperative behavior.

  10. Alkali metal nitrate purification

    DOEpatents

    Fiorucci, Louis C.; Morgan, Michael J.

    1986-02-04

    A process is disclosed for removing contaminants from impure alkali metal nitrates containing them. The process comprises heating the impure alkali metal nitrates in solution form or molten form at a temperature and for a time sufficient to effect precipitation of solid impurities and separating the solid impurities from the resulting purified alkali metal nitrates. The resulting purified alkali metal nitrates in solution form may be heated to evaporate water therefrom to produce purified molten alkali metal nitrates suitable for use as a heat transfer medium. If desired, the purified molten form may be granulated and cooled to form discrete solid particles of purified alkali metal nitrates.

  11. Milk-alkali syndrome

    MedlinePlus

    ... this page: //medlineplus.gov/ency/article/000332.htm Milk-alkali syndrome To use the sharing features on this page, please enable JavaScript. Milk-alkali syndrome is a condition in which there ...

  12. 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}.

  13. Alkali-metal azides interacting with metal-organic frameworks.

    PubMed

    Armata, Nerina; Cortese, Remedios; Duca, Dario; Triolo, Roberto

    2013-01-14

    Interactions between alkali-metal azides and metal-organic framework (MOF) derivatives, namely, the first and third members of the isoreticular MOF (IRMOF) family, IRMOF-1 and IRMOF-3, are studied within the density functional theory (DFT) paradigm. The investigations take into account different models of the selected IRMOFs. The mutual influence between the alkali-metal azides and the π rings or Zn centers of the involved MOF derivatives are studied by considering the interactions both of the alkali-metal cations with model aromatic centers and of the alkali-metal azides with distinct sites of differently sized models of IRMOF-1 and IRMOF-3. Several exchange and correlation functionals are employed to calculate the corresponding interaction energies. Remarkably, it is found that, with increasing alkali-metal atom size, the latter decrease for cations interacting with the π-ring systems and increase for the azides interacting with the MOF fragments. The opposite behavior is explained by stabilization effects on the azide moieties and determined by the Zn atoms, which constitute the inorganic vertices of the IRMOF species. Larger cations can, in fact, coordinate more efficiently to both the aromatic center and the azide anion, and thus stabilizing bridging arrangements of the azide between one alkali-metal and two Zn atoms in an η(2) coordination mode are more favored. PMID:23161861

  14. Electrochemical cell utilizing molten alkali metal electrode-reactant

    DOEpatents

    Virkar, Anil V.; Miller, Gerald R.

    1983-11-04

    An improved electrochemical cell comprising an additive-modified molten alkali metal electrode-reactant and/or electrolyte is disclosed. Various electrochemical cells employing a molten alkali metal, e.g., sodium, electrode in contact with a cationically conductive ceramic membrane experience a lower resistance and a lower temperature coefficient of resistance whenever small amounts of selenium are present at the interface of the electrolyte and the molten alkali metal. Further, cells having small amounts of selenium present at the electrolyte-molten metal interface exhibit less degradation of the electrolyte under long term cycling conditions.

  15. High-temperature corrosion of silicon nitride and mixed alkali effect

    NASA Astrophysics Data System (ADS)

    Jordache, Madeline K.

    Corrosion and associated degradation of silicon nitride (Si3N 4) remains an obstacle to its utilization in high-temperature turbines. This research consists of three interrelated components: comparative and comprehensive study of the oxidation behavior of three types of Si3N4 (turbine-grade Kyocera SN 282 sintered with Lu2O3, Toshiba TSN 03-NH with Y2O3/Al2O3, and Norton NBD 200 with MgO) in dry O2; investigation of the role of Na and Cs in the corrosion resistance of SN 282; and exploration of the mixed alkali effect in improving the corrosion resistance of SN Si3N 4. SN 282, TSN 03-NH, and NBD 200 all follow a parabolic oxidation rate law when exposed in dry O2 at 930°C--1200°C, indicating a diffusion-limited oxidation process. The oxidation rate decreases in order of NBD 200, TSN 03-NH, and SN 282 due to increased crystallinity and refractoriness of the intergranular phases. The activation energies for oxidation of NBD 200, TSN 03-NH, and SN 282 are 259, 205, 107 KJ/mol, respectively. Inward diffusion of molecular oxygen O2 through the oxide layer is the rate-controlling step for oxidation of SN 282. In contrast, outward diffusion of additive cations in the underlying Si3N4 is the rate-limiting mechanism for oxidation of TSN 03-NH and NBD 200. Na and Cs, separately introduced in vapor form of the corresponding nitrates, accelerate the corrosion of SN 282 due to their fluxing effect on the oxide, leading to rapid diffusion of O2. The adverse effect on the corrosion resistance of SN 282 is more pronounced in Cs than in Na that can be attributed to the larger negative Gibbs free energy for dissolution of SiO2 in Cs silicate than in Na silicate. Co-introduction of Na and Cs via vapor mixtures of their nitrates at a fixed alkali concentration but varying Na/Cs ratios revealed the presence of the mixed alkali effect in corrosion for the first time, i.e., the addition of a dissimilar alkali species reduces the overall detrimental effect on the corrosion resistance of

  16. Structural modulation of molybdenyl iodate architectures by alkali metal cations in AMoO3(IO3) (A = K, Rb, Cs): a facile route to new polar materials with large SHG responses.

    PubMed

    Sykora, Richard E; Ok, Kang Min; Halasyamani, P Shiv; Albrecht-Schmitt, Thomas E

    2002-03-01

    Three new molybdenyl iodates, KMoO3(IO3) (1), RbMoO3(IO3) (2), and CsMoO3(IO3) (3), have been prepared through the hydrothermal reactions of MoO3 with AIO4 (A = K, Rb, or Cs) at 180 C. These compounds are isolated as nearly colorless, air-stable crystals. Single-crystal X-ray diffraction experiments reveal that 1 possesses a corrugated layered structure constructed from molybdenum oxide chains that are bridged by iodate anions. The puckering of the layers is caused by the alignment of bent molybdenyl (MoO2(2+)) groups along one side of the molybdenum oxide chains. The K+ cations separate these layers from one another and serve to balance charge. In contrast, compounds 2 and 3, which are isostructural, form three-dimensional structures with small cavities filled with Rb+ or Cs+ cations. The differences between the structures of 1 and those of 2 and 3 are due to rotation of the molybdenyl units as translation occurs down the molybdenum oxide chains in order to accommodate the increased size of the Rb+ and Cs+ cations. This rotation allows for the iodate anions to bridge the molybdenum oxide chains in an additional dimension, creating a three-dimensional network structure. Furthermore, while 1 crystallizes in a centrosymmetric space group, 2 and 3 crystallize in polar space groups. Second-harmonic generation measurements on 2 and 3 show large responses of 400x alpha-quartz. Differential scanning calorimetry measurements demonstrate that 2 and 3 are thermally stable to 494 and 486 C, respectively. UV-vis diffuse reflectance spectra of these compounds show a high degree of transparency from 1 to 3 eV and a band gap of 3.1 eV. PMID:11866608

  17. (abstract) Fundamental Mechanisms of Electrode Kinetics and Alkali Metal Atom Transport at the Alkali Beta'-Alumina/Porous Electrode/Alkali Metal Vapor Three Phase Boundary

    NASA Technical Reports Server (NTRS)

    Williams, R. M.; Jeffries-Nakamura, B.; Ryan, M. A.; Underwood, M. L.; O'Connor, D.; Kisor, A.; Kikkert, S. K.

    1993-01-01

    The mechanisms of electrode kinetics and mass transport of alkali metal oxidation and alkali metal cation reduction at the solid electrolyte/porous electrode boundary as well as alkali metal transport through porous metal electrodes has important applications in optimizing device performance in alkali metal thermal to electric converter (AMTEC) cells which are high temperature, high current density electrochemical cells. Basic studies of these processes also affords the opportunity to investigate a very basic electrochemical reaction over a wide range of conditions; and a variety of mass transport modes at high temperatures via electrochemical techniques. The temperature range of these investigations covers 700K to 1240K; the alkali metal vapor pressures range from about 10(sup -2) to 10(sup 2) Pa; and electrodes studied have included Mo, W, Mo/Na(sub 2)MoO(sub 4), W/Na(sub 2)WO(sub 4), WPt(sub x), and WRh(sub x) (1.0 < x < 6.0 ) with Na at Na-beta'-alumina, and Mo with K at K-beta'-alumina. Both liquid metal/solid electrolyte/alkali metal vapor and alkali metal vapor/solid electrolyte/vapor cells have been used to characterize the reaction and transport processes. We have previously reported evidence of ionic, free molecular flow, and surface transport of sodium in several types of AMTEC electrodes.

  18. K{sub 2}NaOsO{sub 5.5} and K{sub 3}NaOs{sub 2}O{sub 9}: The first osmium perovskites containing alkali cations at the 'A' site

    SciTech Connect

    Mogare, Kailash M.; Klein, Wilhelm; Jansen, Martin

    2012-07-15

    K{sub 2}NaOsO{sub 5.5} and K{sub 3}NaOs{sub 2}O{sub 9} were obtained from solid-state reactions of potassium superoxide, sodium peroxide and osmium metal at elevated oxygen pressures. K{sub 2}NaOsO{sub 5.5} crystallizes as an oxygen-deficient cubic double perovskite in space group Fm3{sup Macron }m with a=8.4184(5) A and contains isolated OsO{sub 6} octahedra. K{sub 3}NaOs{sub 2}O{sub 9} crystallizes hexagonally in P6{sub 3}/mmc with a=5.9998(4) A and c=14.3053(14) A. K{sub 3}NaOs{sub 2}O{sub 9} consists of face sharing Os{sub 2}O{sub 9} pairs of octahedra. According to magnetic measurements K{sub 2}NaOsO{sub 5.5} is diamagnetic, whereas K{sub 3}NaOs{sub 2}O{sub 9} displays strong antiferromagnetic coupling (T{sub N}=140 K), indicating enhanced magnetic interactions within the octahedral pair. - Graphical abstract: High oxidation states of Os, obtained by high oxygen pressure synthesis, are accommodated in double and triple perovskite matrices. K{sub 3}NaOs{sub 2}O{sub 9} displays enhanced magnetic interactions. Highlights: Black-Right-Pointing-Pointer New osmates containing highly oxidized Os were obtained by high O{sub 2} pressure synthesis. Black-Right-Pointing-Pointer High oxidation states of Os are accommodated in double and triple perovskite matrices. Black-Right-Pointing-Pointer Both compounds represent the first Os perovskites with an alkali metal at the A site. Black-Right-Pointing-Pointer K{sub 3}NaOs{sub 2}O{sub 9} displays enhanced magnetic interactions within the octahedral pair.

  19. Alkali metal ionization detector

    DOEpatents

    Bauerle, James E.; Reed, William H.; Berkey, Edgar

    1978-01-01

    Variations in the conventional filament and collector electrodes of an alkali metal ionization detector, including the substitution of helical electrode configurations for either the conventional wire filament or flat plate collector; or, the substitution of a plurality of discrete filament electrodes providing an in situ capability for transferring from an operationally defective filament electrode to a previously unused filament electrode without removing the alkali metal ionization detector from the monitored environment. In particular, the helical collector arrangement which is coaxially disposed about the filament electrode, i.e. the thermal ionizer, provides an improved collection of positive ions developed by the filament electrode. The helical filament design, on the other hand, provides the advantage of an increased surface area for ionization of alkali metal-bearing species in a monitored gas environment as well as providing a relatively strong electric field for collecting the ions at the collector electrode about which the helical filament electrode is coaxially positioned. Alternatively, both the filament and collector electrodes can be helical. Furthermore, the operation of the conventional alkali metal ionization detector as a leak detector can be simplified as to cost and complexity, by operating the detector at a reduced collector potential while maintaining the sensitivity of the alkali metal ionization detector adequate for the relatively low concentration of alkali vapor and aerosol typically encountered in leak detection applications.

  20. Alkali slurry ozonation to produce a high capacity nickel battery material

    DOEpatents

    Jackovitz, John F.; Pantier, Earl A.

    1984-11-06

    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.

  1. Apparatus enables accurate determination of alkali oxides in alkali metals

    NASA Technical Reports Server (NTRS)

    Dupraw, W. A.; Gahn, R. F.; Graab, J. W.; Maple, W. E.; Rosenblum, L.

    1966-01-01

    Evacuated apparatus determines the alkali oxide content of an alkali metal by separating the metal from the oxide by amalgamation with mercury. The apparatus prevents oxygen and moisture from inadvertently entering the system during the sampling and analytical procedure.

  2. Alkalis and Skin.

    PubMed

    Greenwood, John E; Tan, Jin Lin; Ming, Justin Choong Tzen; Abell, Andrew D

    2016-01-01

    The aim of this editorial is to provide an overview of the chemical interactions occurring in the skin of our patients on contact with alkaline agents. Strongly basic alkali is highly aggressive and will readily hydrolyze (or cleave) key biological molecules such as lipids and proteins. This phenomenon is known as saponification in the case of lipids and liquefactive denaturation for peptides and proteins. A short section on current first-aid concepts is included. A better understanding of the basic science behind alkali burns will make us better teachers and provide an insight into the urgency needed in treating these common and dangerous chemical injuries. PMID:26182072

  3. Alkali metal ion battery with bimetallic electrode

    SciTech Connect

    Boysen, Dane A; Bradwell, David J; Jiang, Kai; Kim, Hojong; Ortiz, Luis A; Sadoway, Donald R; Tomaszowska, Alina A; Wei, Weifeng; Wang, Kangli

    2015-04-07

    Electrochemical cells having molten electrodes having an alkali metal provide receipt and delivery of power by transporting atoms of the alkali metal between electrode environments of disparate chemical potentials through an electrochemical pathway comprising a salt of the alkali metal. The chemical potential of the alkali metal is decreased when combined with one or more non-alkali metals, thus producing a voltage between an electrode comprising the molten the alkali metal and the electrode comprising the combined alkali/non-alkali metals.

  4. Interfacial tension in immiscible mixtures of alkali halides.

    PubMed

    Lockett, Vera; Rukavishnikova, Irina V; Stepanov, Victor P; Tkachev, Nikolai K

    2010-02-01

    The interfacial tension of the liquid-phase interface in seven immiscible reciprocal ternary mixtures of lithium fluoride with the following alkali halides: CsCl, KBr, RbBr, CsBr, KI, RbI, and CsI was measured using the cylinder weighing method over a wide temperature range. It was shown that for all mixtures the interfacial tension gradually decreases with growing temperature. The interfacial tension of the reciprocal ternary mixtures at a given temperature increases both with the alkali cation radius (K(+) < Rb(+) < Cs(+)) and with the radius of the halogen anion (Cl(-) < Br(-) < I(-)). PMID:20094678

  5. Methods of recovering alkali metals

    DOEpatents

    Krumhansl, James L; Rigali, Mark J

    2014-03-04

    Approaches for alkali metal extraction, sequestration and recovery are described. For example, a method of recovering alkali metals includes providing a CST or CST-like (e.g., small pore zeolite) material. The alkali metal species is scavenged from the liquid mixture by the CST or CST-like material. The alkali metal species is extracted from the CST or CST-like material.

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

  7. Ion Pairing in Alkali Nitrate Electrolyte Solutions.

    PubMed

    Xie, Wen Jun; Zhang, Zhen; Gao, Yi Qin

    2016-03-10

    In this study, we investigate the thermodynamics of alkali nitrate salt solutions, especially the formation of contact ion pairs between alkali cation and nitrate anion. The ion-pairing propensity shows an order of LiNO3 < NaNO3 < KNO3. Such results explain the salt activity coefficients and suggest that the empirical "law of matching water affinity" is followed by these alkali nitrate salt solutions. The spatial patterns of contact ion pairs are different in the three salt solutions studied here: Li(+) forms the contact ion pair with only one oxygen of the nitrate while Na(+) and K(+) can also be shared by two oxygens of the nitrate. In reproducing the salt activity coefficient using Kirkwood-Buff theory, we find that it is essential to include electronic polarization for Li(+) which has a high charge density. The electronic continuum correction for nonpolarizable force field significantly improves the agreement between the calculated activity coefficients and their experimental values. This approach also improves the performance of the force field on salt solubility. From these two aspects, this study suggests that electronic continuum correction can be a promising approach to force-field development for ions with high charge densities. PMID:26901167

  8. Alkali Metal Variation and Twisting of the FeNNFe Core in Bridging Diiron Dinitrogen Complexes.

    PubMed

    McWilliams, Sean F; Rodgers, Kenton R; Lukat-Rodgers, Gudrun; Mercado, Brandon Q; Grubel, Katarzyna; Holland, Patrick L

    2016-03-21

    Alkali metal cations can interact with Fe-N2 complexes, potentially enhancing back-bonding or influencing the geometry of the iron atom. These influences are relevant to large-scale N2 reduction by iron, such as in the FeMoco of nitrogenase and the alkali-promoted Haber-Bosch process. However, to our knowledge there have been no systematic studies of a large range of alkali metals regarding their influence on transition metal-dinitrogen complexes. In this work, we varied the alkali metal in [alkali cation]2[LFeNNFeL] complexes (L = bulky β-diketiminate ligand) through the size range from Na(+) to K(+), Rb(+), and Cs(+). The FeNNFe cores have similar Fe-N and N-N distances and N-N stretching frequencies despite the drastic change in alkali metal cation size. The two diketiminates twist relative to one another, with larger dihedral angles accommodating the larger cations. In order to explain why the twisting has so little influence on the core, we performed density functional theory calculations on a simplified LFeNNFeL model, which show that the two metals surprisingly do not compete for back-bonding to the same π* orbital of N2, even when the ligand planes are parallel. This diiron system can tolerate distortion of the ligand planes through compensating orbital energy changes, and thus, a range of ligand orientations can give very similar energies. PMID:26925968

  9. Chlor-Alkali Technology.

    ERIC Educational Resources Information Center

    Venkatesh, S.; Tilak, B. V.

    1983-01-01

    Chlor-alkali technology is one of the largest electrochemical industries in the world, the main products being chlorine and caustic soda (sodium hydroxide) generated simultaneously by the electrolysis of sodium chloride. This technology is reviewed in terms of electrochemical principles and manufacturing processes involved. (Author/JN)

  10. Alkali oxide-tantalum oxide and alkali oxide-niobium oxide ionic conductors

    NASA Technical Reports Server (NTRS)

    Roth, R. S.; Parker, H. S.; Brower, W. S.; Minor, D.

    1974-01-01

    A search was made for new cationic conducting phases in alkali-tantalate and niobate systems. The phase equilibrium diagrams were constructed for the six binary systems Nb2O5-LiNbO3, Nb2O5-NaNbO3, Nb2O5-KNbO3, Ta2O5-NaTaO3, Ta2O5-LiTaO3, and Ta2O5-KTaO3. Various other binary and ternary systems were also examined. Pellets of nineteen phases were evaluated (by the sponsoring agency) by dielectric loss measurements. Attempts were made to grow large crystals of eight different phases. The system Ta2O5-KTaO3 contains at least three phases which showed peaks in dielectric loss vs. temperature. All three contain structures related to the tungsten bronzes with alkali ions in non-stoichiometric crystallographic positions.

  11. Alkali absorption and citrate excretion in calcium nephrolithiasis

    NASA Technical Reports Server (NTRS)

    Sakhaee, K.; Williams, R. H.; Oh, M. S.; Padalino, P.; Adams-Huet, B.; Whitson, P.; Pak, C. Y.

    1993-01-01

    The role of net gastrointestinal (GI) alkali absorption in the development of hypocitraturia was investigated. The net GI absorption of alkali was estimated from the difference between simple urinary cations (Ca, Mg, Na, and K) and anions (Cl and P). In 131 normal subjects, the 24 h urinary citrate was positively correlated with the net GI absorption of alkali (r = 0.49, p < 0.001). In 11 patients with distal renal tubular acidosis (RTA), urinary citrate excretion was subnormal relative to net GI alkali absorption, with data from most patients residing outside the 95% confidence ellipse described for normal subjects. However, the normal relationship between urinary citrate and net absorbed alkali was maintained in 11 patients with chronic diarrheal syndrome (CDS) and in 124 stone-forming patients devoid of RTA or CDS, half of whom had "idiopathic" hypocitraturia. The 18 stone-forming patients without RTA or CDS received potassium citrate (30-60 mEq/day). Both urinary citrate and net GI alkali absorption increased, yielding a significantly positive correlation (r = 0.62, p < 0.0001), with the slope indistinguishable from that of normal subjects. Thus, urinary citrate was normally dependent on the net GI absorption of alkali. This dependence was less marked in RTA, confirming the renal origin of hypocitraturia. However, the normal dependence was maintained in CDS and in idiopathic hypocitraturia, suggesting that reduced citrate excretion was largely dietary in origin as a result of low net alkali absorption (from a probable relative deficiency of vegetables and fruits or a relative excess of animal proteins).

  12. Hydrothermal alkali metal recovery process

    DOEpatents

    Wolfs, Denise Y.; Clavenna, Le Roy R.; Eakman, James M.; Kalina, Theodore

    1980-01-01

    In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by treating them with a calcium or magnesium-containing compound in the presence of water at a temperature between about 250.degree. F. and about 700.degree. F. and in the presence of an added base to establish a pH during the treatment step that is higher than would otherwise be possible without the addition of the base. During the treating process the relatively high pH facilitates the conversion of water-insoluble alkali metal compounds in the alkali metal residues into water-soluble alkali metal constituents. The resultant aqueous solution containing water-soluble alkali metal constituents is then separated from the residue solids, which consist of the treated particles and any insoluble materials formed during the treatment step, and recycled to the gasification process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst. Preferably, the base that is added during the treatment step is an alkali metal hydroxide obtained by water washing the residue solids produced during the treatment step.

  13. Efficient destruction of CF4 through in situ generation of alkali metals from heated alkali halide reducing mixtures.

    PubMed

    Lee, Myung Churl; Choi, Wonyong

    2002-03-15

    Perfluorocarbons (PFCs) are the most potent green house gases that are very recalcitrant at destruction. An effective way of converting PFCs using hot solid reagents into safe products has been recently introduced. By investigating the thermal reductive destruction of tetrafluoromethane (CF4) we provided new insight and more physicochemical consideration on this novel process. The complete destruction of CF4was successfully achieved by flowing the gas through a heated reagent bed (400-950 degrees C) that contained powder mixtures of alkali halides, CaO, and Si. The silicon acted as a reducing agent of alkali halides for the in-situ production of alkali metals, and the calcium oxide played the role of a halide ion acceptor. The absence of any single component in this ternary mixture drastically reduced the destruction efficiency of CF4. The CF4 destruction efficiencies with the solid reagent containing the alkali halide, MX, increased in the order of Li approximately Na < K < Cs for alkali cations and I < Br < Cl < F for halide anions. This trend agreed with the endothermicity of the alkali metal generation reaction: the higher the endothermicity, the lower the destruction efficiency. Alkali metal generation was indirectly detected by monitoring H2 production from its reaction with water. The production of alkali metals increased with NaF, KF, and CsF in this order. The CsF/CaO/Si system exhibited the complete destruction of CF4 at as low as 600 degrees C. The solid product analysis by X-ray diffraction (XRD) showed the formation of CaF2 and the depletion of Si with black carbon particles formed in the solid reagent residue. No CO/CO2 and toxic HF and SiF4 formation were detected in the exhaust gas. PMID:11944694

  14. Diversity and Mechanisms of Alkali Tolerance in Lactobacilli▿

    PubMed Central

    Sawatari, Yuki; Yokota, Atsushi

    2007-01-01

    We determined the maximum pH that allows growth (pHmax) for 34 strains of lactobacilli. High alkali tolerance was exhibited by strains of Lactobacillus casei, L. paracasei subsp. tolerans, L. paracasei subsp. paracasei, L. curvatus, L. pentosus, and L. plantarum that originated from plant material, with pHmax values between 8.5 and 8.9. Among these, L. casei NRIC 1917 and L. paracasei subsp. tolerans NRIC 1940 showed the highest pHmax, at 8.9. Digestive tract isolates of L. gasseri, L. johnsonii, L. reuteri, L. salivarius subsp. salicinius, and L. salivarius subsp. salivarius exhibited moderate alkali tolerance, with pHmax values between 8.1 and 8.5. Dairy isolates of L. delbrueckii subsp. bulgaricus, L. delbrueckii subsp. lactis, and L. helveticus exhibited no alkali tolerance, with pHmax values between 6.7 and 7.1. Measurement of the internal pH of representative strains revealed the formation of transmembrane proton gradients (ΔpH) in a reversed direction (i.e., acidic interior) at alkaline external-pH ranges, regardless of their degrees of alkali tolerance. Thus, the reversed ΔpH did not determine alkali tolerance diversity. However, the ΔpH contributed to alkali tolerance, as the pHmax values of several strains decreased with the addition of nigericin, which dissipates ΔpH. Although neutral external-pH values resulted in the highest glycolysis activity in the presence of nigericin regardless of alkali tolerance, substantial glucose utilization was still detected in the alkali-tolerant strains, even in a pH range of between 8.0 and 8.5, at which the remaining strains lost most activity. Therefore, the alkali tolerance of glycolysis reactions contributes greatly to the determination of alkali tolerance diversity. PMID:17449704

  15. Simple model potential and model wave functions for (H-alkali)+ and (alkali-alkali)+ ions

    NASA Astrophysics Data System (ADS)

    Patil, S. H.; Tang, K. T.

    2000-07-01

    A simple model potential is proposed to describe the interaction of a valence electron with the alkali core, which incorporates the correct asymptotic behavior in terms of dipolar polarizabilities, and the short-range exchange effects in terms of a hard core adjusted to give the correct energy for the valence electron. Based on this potential, simple wave functions are developed to describe the (H-alkali)+ and (alkali-alkali)+ ions. These wave functions exhibit some important structures of the ions, and provide a universal description of the properties of all (H-alkali)+ and (alkali-alkali)+ ions, in particular, the equilibrium separations of the nuclei and the corresponding dissociation energies. They also allow us to calculate the dipolar polarizabilities of Li2+, Na2+, K2+, Rb2+, and Cs2+.

  16. Alkali-vapor lasers

    NASA Astrophysics Data System (ADS)

    Zweiback, J.; Komashko, A.; Krupke, W. F.

    2010-02-01

    We report on the results from several of our alkali laser systems. We show highly efficient performance from an alexandrite-pumped rubidium laser. Using a laser diode stack as a pump source, we demonstrate up to 145 W of average power from a CW system. We present a design for a transversely pumped demonstration system that will show all of the required laser physics for a high power system.

  17. (abstract) Experimental and Modeling Studies of the Exchange Current at the Alkali Beta'-Alumina/Porous Electrode/Alkali Metal Vapor Three Phase Boundary

    NASA Technical Reports Server (NTRS)

    Williams, R. M.; Jeffries-Nakamura, B.; Ryan, M. A.; Underwood, M. L.; O'Connor, D.; Kikkert, S.

    1993-01-01

    The microscopic mechanism of the alkali ion-electron recombination reaction at the three phase boundary zone formed by a porous metal electrode in the alkali vapor on the surface of an alkali beta'-alumina solid electrolyte (BASE) ceramic has been studied by comparison of the expected rates for the three simplest reaction mechanisms with known temperature dependent rate data; and the physical parameters of typical porous metal electrode/BASE/alkali metal vapor reaction zones. The three simplest reactions are tunneling of electrons from the alkali coated electrode to a surface bound alkali metal ion; emission of an electron from the electrode with subsequent capture by a surface bound alkali metal ion; and thermal emission of an alkali cation from the BASE and its capture on the porous metal electrode surface where it may recombine with an electron. Only the first reaction adequately accounts for both the high observed rate and its temperature dependence. New results include crude modeling of simple, one step, three phase, solid/solid/gas electrochemical reaction.

  18. Hyaline membrane disease, alkali, and intraventricular haemorrhage.

    PubMed Central

    Wigglesworth, J S; Keith, I H; Girling, D J; Slade, S A

    1976-01-01

    which distinguishes babies dying with GLH and IVH from other groups of babies with HMD. Although the causal nature of this association remains unproved, it seems justifiable to lrge caution in alkali usage. PMID:1008580

  19. High pressure Raman and single crystal X-ray diffraction of the alkali/calcium carbonate, shortite

    NASA Astrophysics Data System (ADS)

    Williams, Q. C.; Vennari, C.; O'Bannon, E. F., III

    2015-12-01

    Raman and synchrotron-based single crystal x-ray diffraction data have been collected on shortite (Na2Ca2(CO3)3) up to 10 GPa at 300 K. Shortite is of geological importance due to its presence in the ground-mass of kimberlites, and the alkaline-/carbon-rich character of kimberlitic eruptions. This investigation focuses on shortite's high pressure behavior and is relevant to the behavior of alkali-carbonate systems within Earth's upper mantle. X-ray data demonstrate that shortite's symmetry remains stable at high pressures—retaining orthorhombic C crystal system (Amm2) up to 10 GPa; diffraction data show a 12% volume decrease from room pressure, and a bulk modulus of 71.0(3) GPa. These also demonstrate that the c-axis is twice as compressible as the a- and b-axes. This anisotropic compression is likely due to the orientation of the relatively stiff carbonate groups, a third of which are oriented close to the plane of the a- and b-axes, c axis compression primarily involves the compaction of the 9-fold coordinate sodium and calcium polyhedral. The two distinct carbonate sites within the unit cell give rise to two Raman symmetric stretching modes of the symmetric stretch; the carbonate group stretching vibration which is close to in plane with the a- and b-axes shifts at 3.75 cm-1/GPa as opposed to the carbonate groups which is closer to in plane with the b- and c-axes which shift at 4.25 cm-1/GPa. This furthers evidence for anisotropic compression observed using x-ray diffraction--as the carbonate in plane with the a- and b-axes is compressed, the strength of oxygen bonds along the c-axis with the cations increases, thus decreasing the pressure shift of the mode. The out of plane bending vibration shifts at -0.48 cm-1/GPa, indicating an enhanced interaction of the oxygens with the cations. The multiple in plane bending modes all shift positively, as do at the low frequency lattice modes, indicating that major changes in bonding do not occur up to 10 GPa. The data

  20. [PALEOPATHOLOGY OF HUMAN REMAINS].

    PubMed

    Minozzi, Simona; Fornaciari, Gino

    2015-01-01

    Many diseases induce alterations in the human skeleton, leaving traces of their presence in ancient remains. Paleopathological examination of human remains not only allows the study of the history and evolution of the disease, but also the reconstruction of health conditions in the past populations. This paper describes the most interesting diseases observed in skeletal samples from the Roman Imperial Age necropoles found in urban and suburban areas of Rome during archaeological excavations in the last decades. The diseases observed were grouped into the following categories: articular diseases, traumas, infections, metabolic or nutritional diseases, congenital diseases and tumours, and some examples are reported for each group. Although extensive epidemiological investigation in ancient skeletal records is impossible, the palaeopathological study allowed to highlight the spread of numerous illnesses, many of which can be related to the life and health conditions of the Roman population. PMID:27348992

  1. Propellant-remaining modeling

    NASA Technical Reports Server (NTRS)

    Torgovitsky, S.

    1991-01-01

    A successful satellite mission is predicted upon the proper maintenance of the spacecraft's orbit and attitude. One requirement for planning and predicting the orbit and attitude is the accurate estimation of the propellant remaining onboard the spacecraft. Focuss is on the three methods that were developed for calculating the propellant budget: the errors associated with each method and the uncertainties in the variables required to determine the propellant remaining that contribute to these errors. Based on these findings, a strategy is developed for improved propellant-remaining estimation. The first method is based on Boyle's law, which related the values of pressure, volume, and temperature (PVT) of an ideal gas. The PVT method is used for the monopropellant and the bipropellant engines. The second method is based on the engine performance tests, which provide data that relate thrust and specific impulse associated with a propellant tank to that tank's pressure. Two curves representing thrust and specific impulse as functions of pressure are then generated using a polynomial fit on the engine performance data. The third method involves a computer simulation of the propellant system. The propellant flow is modeled by creating a conceptual model of the propulsion system configuration, taking into account such factors as the propellant and pressurant tank characteristics, thruster functionality, and piping layout. Finally, a thrust calibration technique is presented that uses differential correction with the computer simulation method of propellant-remaining modeling. Thrust calibration provides a better assessment of thruster performance and therefore enables a more accurate estimation of propellant consumed during a given maneuver.

  2. PROCESS OF RECOVERING ALKALI METALS

    DOEpatents

    Wolkoff, J.

    1961-08-15

    A process is described of recovering alkali metal vapor by sorption on activated alumina, activated carbon, dehydrated zeolite, activated magnesia, or Fuller's earth preheated above the vaporization temperature of the alkali metal and subsequent desorption by heating the solvent under vacuum. (AEC)

  3. Preparation of alkali metal dispersions

    NASA Technical Reports Server (NTRS)

    Rembaum, A.; Landel, R. F. (Inventor)

    1968-01-01

    A method is described for producing alkali metal dispersions of high purity. The dispersions are prepared by varying the equilibrium solubility of the alkali metal in a suitable organic solvent in the presence of aromatic hydrocarbons. The equilibrium variation is produced by temperature change. The size of the particles is controlled by controlling the rate of temperature change.

  4. Purification of alkali metal nitrates

    DOEpatents

    Fiorucci, Louis C.; Gregory, Kevin M.

    1985-05-14

    A process is disclosed for removing heavy metal contaminants from impure alkali metal nitrates containing them. The process comprises mixing the impure nitrates with sufficient water to form a concentrated aqueous solution of the impure nitrates, adjusting the pH of the resulting solution to within the range of between about 2 and about 7, adding sufficient reducing agent to react with heavy metal contaminants within said solution, adjusting the pH of the solution containing reducing agent to effect precipitation of heavy metal impurities and separating the solid impurities from the resulting purified aqueous solution of alkali metal nitrates. The resulting purified solution of alkali metal nitrates may be heated to evaporate water therefrom to produce purified molten alkali metal nitrate suitable for use as a heat transfer medium. If desired, the purified molten form may be granulated and cooled to form discrete solid particles of alkali metal nitrates.

  5. Alkali metal and alkali earth metal gadolinium halide scintillators

    DOEpatents

    Bourret-Courchesne, Edith; Derenzo, Stephen E.; Parms, Shameka; Porter-Chapman, Yetta D.; Wiggins, Latoria K.

    2016-08-02

    The present invention provides for a composition comprising an inorganic scintillator comprising a gadolinium halide, optionally cerium-doped, having the formula A.sub.nGdX.sub.m:Ce; wherein A is nothing, an alkali metal, such as Li or Na, or an alkali earth metal, such as Ba; X is F, Br, Cl, or I; n is an integer from 1 to 2; m is an integer from 4 to 7; and the molar percent of cerium is 0% to 100%. The gadolinium halides or alkali earth metal gadolinium halides are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

  6. Predicting the remaining service life of concrete

    SciTech Connect

    Clifton, J.F.

    1991-11-01

    Nuclear power plants are providing, currently, about 17 percent of the U.S. electricity and many of these plants are approaching their licensed life of 40 years. The U.S. Nuclear Regulatory Commission and the Department of Energy`s Oak Ridge National Laboratory are carrying out a program to develop a methodology for assessing the remaining safe-life of the concrete components and structures in nuclear power plants. This program has the overall objective of identifying potential structural safety issues, as well as acceptance criteria, for use in evaluations of nuclear power plants for continued service. The National Institute of Standards and Technology (NIST) is contributing to this program by identifying and analyzing methods for predicting the remaining life of in-service concrete materials. This report examines the basis for predicting the remaining service lives of concrete materials of nuclear power facilities. Methods for predicting the service life of new and in-service concrete materials are analyzed. These methods include (1) estimates based on experience, (2) comparison of performance, (3) accelerated testing, (4) stochastic methods, and (5) mathematical modeling. New approaches for predicting the remaining service lives of concrete materials are proposed and recommendations for their further development given. Degradation processes are discussed based on considerations of their mechanisms, likelihood of occurrence, manifestations, and detection. They include corrosion, sulfate attack, alkali-aggregate reactions, frost attack, leaching, radiation, salt crystallization, and microbiological attack.

  7. Upgrading platform using alkali metals

    SciTech Connect

    Gordon, John Howard

    2014-09-09

    A process for removing sulfur, nitrogen or metals from an oil feedstock (such as heavy oil, bitumen, shale oil, etc.) The method involves reacting the oil feedstock with an alkali metal and a radical capping substance. The alkali metal reacts with the metal, sulfur or nitrogen content to form one or more inorganic products and the radical capping substance reacts with the carbon and hydrogen content to form a hydrocarbon phase. The inorganic products may then be separated out from the hydrocarbon phase.

  8. Is Electronegativity a Useful Descriptor for the "Pseudo-Alkali-Metal" NH4?

    SciTech Connect

    Whiteside, Alexander; Xantheas, Sotiris S.; Gutowski, Maciej S.

    2011-11-18

    Molecular ions in the form of "pseudo-atoms" are common structural motifs in chemistry, with properties that are transferrable between different compounds. We have determined the electronegativity of the "pseudo-alkali metal" ammonium (NH4) and evaluated its reliability as a descriptor in comparison to the electronegativities of the alkali metals. The computed properties of its binary complexes with astatine and of selected borohydrides confirm the similarity of NH4 to the alkali metal atoms, although the electronegativity of NH4 is relatively large in comparison to its cationic radius. We paid particular attention to the molecular properties of ammonium (angular anisotropy, geometric relaxation, and reactivity), which can cause deviations from the behaviour expected of a conceptual "true alkali metal" with this electronegativity. These deviations allow for the discrimination of effects associated with the polyatomic nature of NH4.

  9. Is electronegativity a useful descriptor for the pseudo-alkali metal NH4?

    PubMed

    Whiteside, Alexander; Xantheas, Sotiris S; Gutowski, Maciej

    2011-11-18

    Molecular ions in the form of "pseudo-atoms" are common structural motifs in chemistry, with properties that are transferrable between different compounds. We have determined one such property--the electronegativity--for the "pseudo-alkali metal" ammonium (NH(4)), and evaluated its reliability as a descriptor versus the electronegativities of the alkali metals. The computed properties of ammonium's binary complexes with astatine and of selected borohydrides confirm the similarity of NH(4) to the alkali metal atoms, although the electronegativity of NH(4) is relatively large in comparison to its cationic radius. We have paid particular attention to the molecular properties of ammonium (angular anisotropy, geometric relaxation and reactivity), which can cause deviations from the behaviour expected of a conceptual "true alkali metal" with this electronegativity. These deviations allow for the discrimination of effects associated with the molecular nature of NH(4). PMID:21928287

  10. The cation-π interaction.

    PubMed

    Dougherty, Dennis A

    2013-04-16

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

  11. 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

  12. Coordination effect-regulated CO2 capture with an alkali metal onium salts/crown ether system

    SciTech Connect

    Yang, Zhen-Zhen; Jiang, Deen; Zhu, Xiang; Tian, Chengcheng; Brown, Suree; Do-Thanh, Chi-Linh; He, Liang-Nian; Dai, Sheng

    2014-01-01

    A coordination effect was employed to realize equimolar CO2 absorption, adopting easily synthesized amino group containing absorbents (alkali metal onium salts). The essence of our strategy was to increase the steric hindrance of cations so as to enhance a carbamic acid pathway for CO2 capture. Our easily synthesized alkali metal amino acid salts or phenolates were coordinated with crown ethers, in which highly sterically hindered cations were obtained through a strong coordination effect of crown ethers with alkali metal cations. For example, a CO2 capacity of 0.99 was attained by potassium prolinate/18-crown-6, being characterized by NMR, FT-IR, and quantum chemistry calculations to go through a carbamic acid formation pathway. The captured CO2 can be stripped under very mild conditions (50 degrees C, N-2). Thus, this protocol offers an alternative for the development of technological innovation towards efficient and low energy processes for carbon capture and sequestration.

  13. First-principles study of ternary graphite compounds cointercalated with alkali atoms (Li, Na, and K) and alkylamines towards alkali ion battery applications

    NASA Astrophysics Data System (ADS)

    Ri, Gum-Chol; Yu, Chol-Jun; Kim, Jin-Song; Hong, Song-Nam; Jong, Un-Gi; Ri, Mun-Hyok

    2016-08-01

    First-principles calculations were carried out to investigate the structural, energetic, and electronic properties of ternary graphite compounds cointercalated with alkali atoms (AM = Li, Na, and K) and normal alkylamine molecules (nCx; x = 1, 2, 3, 4), denoted as AM-nCx-GICs. From the optimization of the orthorhombic unit cells for the crystalline compounds, it was found that, with the increase in the atomic number of alkali atoms, the layer separations decrease in contrast to AM-GICs, while the bond lengths between alkali atoms and graphene layer, and nitrogen atom of alkylamine increase. The calculated formation energies and interlayer binding energies of AM-nC3-GICs indicate that the compounds is increasingly stabilized from Li to K, and the energy barriers for migration of alkali atoms suggest that alkali cation with larger ionic radius diffuses more smoothly in graphite, being similar to AM-GICs. Through the analysis of electronic properties, it was established that more extent of electronic charge is transferred from more electropositive alkali atom to the carbon ring of graphene layer, and the hybridization of valence electron orbitals between alkylamine molecules and graphene layer is occurred.

  14. Intermetallic Competition in the Fragmentation of Trimetallic Au-Zn-Alkali Complexes.

    PubMed

    Lang, Johannes; Cayir, Merve; Walg, Simon P; Di Martino-Fumo, Patrick; Thiel, Werner R; Niedner-Schatteburg, Gereon

    2016-02-12

    Cationization is a valuable tool to enable mass spectrometric studies on neutral transition-metal complexes (e.g., homogenous catalysts). However, knowledge of potential impacts on the molecular structure and catalytic reactivity induced by the cationization is indispensable to extract information about the neutral complex. In this study, we cationize a bimetallic complex [AuZnCl3 ] with alkali metal ions (M(+) ) and investigate the charged adducts [AuZnCl3 M](+) by electrospray ionization mass spectrometry (ESI-MS). Infrared multiple photon dissociation (IR-MPD) in combination with density functional theory (DFT) calculations reveal a μ(3) binding motif of all alkali ions to the three chlorido ligands. The cationization induces a reorientation of the organic backbone. Collision-induced dissociation (CID) studies reveal switches of fragmentation channels by the alkali ion and by the CID amplitude. The Li(+) and Na(+) adducts prefer the sole loss of ZnCl2 , whereas the K(+) , Rb(+) , and Cs(+) adducts preferably split off MCl2 ZnCl. Calculated energetics along the fragmentation coordinate profiles allow us to interpret the experimental findings to a level of subtle details. The Zn(2+) cation wins the competition for the nitrogen coordination sites against K(+) , Rb(+) , and Cs(+) , but it loses against Li(+) and Na(+) in a remarkable deviation from a naive hard and soft acids and bases (HSAB) concept. The computations indicate expulsion of MCl2 ZnCl rather than of MCl and ZnCl2 . PMID:26785330

  15. High-temperature interactions of alkali vapors with solids during coal combustion and gasification

    SciTech Connect

    Punjak, W.A.

    1988-01-01

    A temperature and concentration programmed reaction method is used to investigate the mechanism by which organically bound alkali is released from carbonaceous substrates. Vaporization of the alkali is preceded by reduction of oxygen-bearing groups during which CO is generated. A residual amount of alkali remains after complete reduction. This residual level is greater for potassium, indicating that potassium has stronger interactions with graphitic substrates that sodium. Other mineral substrates were exposed to high temperature alkali chloride vapors under both nitrogen and simulated flue gas atmospheres to investigate their potential application as sorbents for the removal of alkali from coal conversion flue gases. The compounds containing alumina and silica are found to readily adsorb alkali vapors and the minerals kaolinite, bauxite and emathlite are identified as promising alkali sorbents. The fundamentals of alkali adsorption on kaolinite, bauxite and emathlite are compared and analyzed both experimentally and through theoretical modeling. The experiments were performed in a microgravimetric reactor system; the sorbents were characterized before and after alkali adsorption using scanning Auger microscopy, X-ray diffraction analysis, mercury porosimetry and atomic emission spectrophotometry. The results show that the process is not a simple physical condensation, but a complex combination of several diffusion steps and reactions.

  16. Aqueous Cation-Amide Binding: Free Energies and IR Spectral Signatures by Ab Initio Molecular Dynamics

    SciTech Connect

    Pluharova, Eva; Baer, Marcel D.; Mundy, Christopher J.; Schmidt, Burkhard; Jungwirth, Pavel

    2014-07-03

    Understanding specific ion effects on proteins remains a considerable challenge. N-methylacetamide serves as a useful proxy for the protein backbone that can be well characterized both experimentally and theoretically. The spectroscopic signatures in the amide I band reflecting the strength of the interaction of alkali cations and alkali earth dications with the carbonyl group remain difficult to assign and controversial to interpret. Herein, we directly compute the IR shifts corresponding to the binding of either sodium or calcium to aqueous N-methylacetamide using ab initio molecular dynamics simulations. We show that the two cations interact with aqueous N-methylacetamide with different affinities and in different geometries. Since sodium exhibits a weak interaction with the carbonyl group, the resulting amide I band is similar to an unperturbed carbonyl group undergoing aqueous solvation. In contrast, the stronger calcium binding results in a clear IR shift with respect to N-methylacetamide in pure water. Support from the Czech Ministry of Education (grant LH12001) is gratefully acknowledged. EP thanks the International Max-Planck Research School for support and the Alternative Sponsored Fellowship program at Pacific Northwest National Laboratory (PNNL). PJ acknowledges the Praemium Academie award from the Academy of Sciences. Calculations of the free energy profiles were made possible through generous allocation of computer time from the North-German Supercomputing Alliance (HLRN). Calculations of vibrational spectra were performed in part using the computational resources in the National Energy Research Supercomputing Center (NERSC) at Lawrence Berkeley National Laboratory. This work was supported by National Science Foundation grant CHE-0431312. CJM is supported by the U.S. Department of Energy`s (DOE) Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. PNNL is operated for the Department of Energy by Battelle. MDB is

  17. Carboxylate Ion Pairing with Alkali-Metal Ions for β-Lactoglobulin and Its Role on Aggregation and Interfacial Adsorption.

    PubMed

    Beierlein, Frank R; Clark, Timothy; Braunschweig, Björn; Engelhardt, Kathrin; Glas, Lena; Peukert, Wolfgang

    2015-04-30

    We report a combined experimental and computational study of the whey protein β-lactoglobulin (BLG) in different electrolyte solutions. Vibrational sum-frequency generation (SFG) and ellipsometry were used to investigate the molecular structure of BLG modified air-water interfaces as a function of LiCl, NaCl, and KCl concentrations. Molecular dynamics (MD) simulations and thermodynamic integration provided details of the ion pairing of protein surface residues with alkali-metal cations. Our results at pH 6.2 indicate that BLG at the air-water interface forms mono- and bilayers preferably at low and high ionic strength, respectively. Results from SFG spectroscopy and ellipsometry are consistent with intimate ion pairing of alkali-metal cations with aspartate and glutamate carboxylates, which is shown to be more effective for smaller cations (Li(+) and Na(+)). MD simulations show not only carboxylate-alkali-metal ion pairs but also ion multiplets with the alkali-metal ion in a bridging position between two or more carboxylates. Consequently, alkali-metal cations can bridge carboxylates not only within a monomer but also between monomers, thus providing an important dimerization mechanism between hydrophilic surface patches. PMID:25825918

  18. A new mechanism for radiation damage processes in alkali halides

    NASA Astrophysics Data System (ADS)

    Dubinko, V. I.; Turkin, A. A.; Vainshtein, D. I.; den Hartog, H. W.

    1999-12-01

    We present a theory of radiation damage formation in alkali halides based on a new mechanism of dislocation climb, which involves the production of VF centers (self-trapped hole neighboring a cation vacancy) as a result of the absorption of H centers of dislocation lines. We consider the evolution of all experimentally observed extended defects: metal colloids, gas bubbles, and vacancy voids. Voids are shown to arise and grow large due to the reaction between F and VF centers at the surface of halogen bubbles. Voids can ignite a back reaction between the radiolytic products resulting in decomposition of the irradiated material.

  19. The alkali-labile linkage between keratan sulphate and protein

    PubMed Central

    Hopwood, John J.; Robinson, H. Clem

    1974-01-01

    Keratan sulphate was isolated from adult intervertebral disc in 90% yield by sequential digestion of the whole tissue with papain, Pronase and Proteus vulgaris chondroitin sulphate lyase. Treatment of this preparation with alkali cleaved a glycosidic bond between N-acetylgalactosamine and threonine and produced, by an alkali-catalysed `peeling' reaction, an unsaturated derivative of N-acetylgalactosamine which reacted as a chromogen in the Morgan–Elson reaction, but remained covalently bonded to the keratan sulphate chain. This derivative was reduced and labelled by alkaline NaB3H4. The substituent at position 3 of N-acetylgalactosamine in the keratan sulphate–protein linkage was identified as a disaccharide, N-acetylneuraminylgalactose, which was isolated from the reaction mixture after alkali treatment. PMID:4281652

  20. MLKL forms cation channels

    PubMed Central

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

    2016-01-01

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

  1. Cation specific binding with protein surface charges.

    PubMed

    Hess, Berk; van der Vegt, Nico F A

    2009-08-11

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

  2. Hydrothermal alkali metal catalyst recovery process

    DOEpatents

    Eakman, James M.; Clavenna, LeRoy R.

    1979-01-01

    In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles primarily in the form of water soluble alkali metal formates by treating the particles with a calcium or magnesium-containing compound in the presence of water at a temperature between about 250.degree. F. and about 700.degree. F. and in the presence of added carbon monoxide. During the treating process the water insoluble alkali metal compounds comprising the insoluble alkali metal residues are converted into water soluble alkali metal formates. The resultant aqueous solution containing water soluble alkali metal formates is then separated from the treated particles and any insoluble materials formed during the treatment process, and recycled to the gasification process where the alkali metal formates serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst. This process permits increased recovery of alkali metal constituents, thereby decreasing the overall cost of the gasification process by reducing the amount of makeup alkali metal compounds necessary.

  3. Electrolytic method to make alkali alcoholates using ion conducting alkali electrolyte/separator

    DOEpatents

    Joshi, Ashok V.; Balagopal, Shekar; Pendelton, Justin

    2011-12-13

    Alkali alcoholates, also called alkali alkoxides, are produced from alkali metal salt solutions and alcohol using a three-compartment electrolytic cell. The electrolytic cell includes an anolyte compartment configured with an anode, a buffer compartment, and a catholyte compartment configured with a cathode. An alkali ion conducting solid electrolyte configured to selectively transport alkali ions is positioned between the anolyte compartment and the buffer compartment. An alkali ion permeable separator is positioned between the buffer compartment and the catholyte compartment. The catholyte solution may include an alkali alcoholate and alcohol. The anolyte solution may include at least one alkali salt. The buffer compartment solution may include a soluble alkali salt and an alkali alcoholate in alcohol.

  4. The calcium-alkali syndrome.

    PubMed

    Arroyo, Mariangeli; Fenves, Andrew Z; Emmett, Michael

    2013-04-01

    The milk-alkali syndrome was a common cause of hypercalcemia, metabolic alkalosis, and renal failure in the early 20th century. It was caused by the ingestion of large quantities of milk and absorbable alkali to treat peptic ulcer disease. The syndrome virtually vanished after introduction of histamine-2 blockers and proton pump inhibitors. More recently, a similar condition called the calcium-alkali syndrome has emerged as a common cause of hypercalcemia and alkalosis. It is usually caused by the ingestion of large amounts of calcium carbonate salts to prevent or treat osteoporosis and dyspepsia. We describe a 78-year-old woman who presented with weakness, malaise, and confusion. She was found to have hypercalcemia, acute renal failure, and metabolic alkalosis. Upon further questioning, she reported use of large amounts of calcium carbonate tablets to treat recent heartburn symptoms. Calcium supplements were discontinued, and she was treated with intravenous normal saline. After 5 days, the calcium and bicarbonate levels normalized and renal function returned to baseline. In this article, we review the pathogenesis of the calcium-alkali syndrome as well as the differences between the traditional and modern syndromes. PMID:23543983

  5. Acid and alkali doped PBI electrolyte in electrochemical system

    NASA Astrophysics Data System (ADS)

    Xing, Baozhong

    was established. In solution the cations and OH- all participate in the transport of current. It is the OH- that breaks the bonds between PBI molecules and enables the cations pass through the membrane. The performance of alkali doped PBI (doped under optimum conditions) in fuel cell as PEM is as good as NafionRTM.

  6. Progress in Understanding Alkali-Alkali Spin Relaxation

    NASA Astrophysics Data System (ADS)

    Erickson, Christopher J.; Happer, William; Chann, Bien; Kadlecek, Stephen; Anderson, L. W.; Walker, Thad G.

    2000-06-01

    In extensive experiments we have shown that a spin interaction with a relatively long correlation time causes much of the spin relaxation in very dense alkali-metal vapors. The spin relaxation is affected by the pressure of the helium or nitrogen buffer gas, although there is little dependence at pressures above one atmosphere. There are substantial differences in the relaxation rates for different isotopes of the same element, for example ^87Rb and ^85Rb. We have completed extensive modeling of how singlet and triplet dimers and doublet trimers of the alkali-metal atoms could cause spin relaxation in dense alkali-metal vapors. In the case of doublet trimers or triplet dimers, we assume the main coupling to the nuclear spins is through the Fermi Contact interaction with the unpaired electrons. Spin loss to the rotation of the molecule is assumed to occur through the electronic spin-rotation and spin-axis (dipole-dipole) interactions for the triplet dimers. For the singlet dimers, we assume that the nuclear spins couple directly to the rotational angular momentum of the molecule through the electric quadrupole interaction. We account for all of the total nuclear spin states that occur for the dimers and trimers. We have also considered the possibility that the collisional breakup and formation rates of the dimers or trimers could saturate with increasing buffer gas pressure. Such saturation occurs in many other unimolecular reactions and is often ascribed to breakup through activated states.

  7. A study on optical properties of poly (ethylene oxide) based polymer electrolyte with different alkali metal iodides

    NASA Astrophysics Data System (ADS)

    Rao, B. Narasimha; Suvarna, R. Padma

    2016-05-01

    Polymer electrolytes were prepared by adding poly (ethylene glycol) dimethyl ether (PEGDME), TiO2 (nano filler), different alkali metal iodide salts RI (R+=Li+, Na+, K+, Rb+, Cs+) and I2 into Acetonitrile gelated with Poly (ethylene oxide) (PEO). Optical properties of poly (ethylene oxide) based polymer electrolytes were studied by FTIR, UV-Vis spectroscopic techniques. FTIR spectrum reveals that the alkali metal cations were coordinated to ether oxygen of PEO. The optical absorption studies were made in the wavelength range 200-800 nm. It is observed that the optical absorption increases with increase in the radius of alkali metal cation. The optical band gap for allowed direct transitions was evaluated using Urbach-edges method. The optical properties such as optical band gap, refractive index and extinction coefficient were determined. The studied polymer materials are useful for solar cells, super capacitors, fuel cells, gas sensors etc.

  8. 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.

  9. Raman spectroscopic investigation of alkali-metal hexachloro compounds of refractory metals

    SciTech Connect

    Kipouros, G.J.; Flint, J.H.; Sadoway, D.R.

    1985-11-06

    The Raman spectra of molten alkali-metal hexachlorozirconate, hexachlorohafnate, hexachloroniobate, and hexachlorotantalate compounds have been obtained in the temperature range 623-1143 K. The results confirm that the refractory metal exists in the form of an octahedrally coordinated complex anion that is stable even in the molten state. For a given refractory metal the frequency of the nu/sub 1/ line increases as the size of the alkali-metal cation decreases. For a given alkali metal the frequency of the nu/sub 1/ line increases as the valence of the refractory metal increases. This last observation may serve as the basis for detecting, by Raman spectroscopy, aliovalent species that may form during the electrolysis of melts containing refractory-metal chlorides. 22 references, 4 figures, 2 tables.

  10. Positron-alkali atom scattering

    NASA Technical Reports Server (NTRS)

    Mceachran, R. P.; Horbatsch, M.; Stauffer, A. D.; Ward, S. J.

    1990-01-01

    Positron-alkali atom scattering was recently investigated both theoretically and experimentally in the energy range from a few eV up to 100 eV. On the theoretical side calculations of the integrated elastic and excitation cross sections as well as total cross sections for Li, Na and K were based upon either the close-coupling method or the modified Glauber approximation. These theoretical results are in good agreement with experimental measurements of the total cross section for both Na and K. Resonance structures were also found in the L = 0, 1 and 2 partial waves for positron scattering from the alkalis. The structure of these resonances appears to be quite complex and, as expected, they occur in conjunction with the atomic excitation thresholds. Currently both theoretical and experimental work is in progress on positron-Rb scattering in the same energy range.

  11. Alkali metal/sulfur battery

    DOEpatents

    Anand, Joginder N.

    1978-01-01

    Alkali metal/sulfur batteries in which the electrolyte-separator is a relatively fragile membrane are improved by providing means for separating the molten sulfur/sulfide catholyte from contact with the membrane prior to cooling the cell to temperatures at which the catholyte will solidify. If the catholyte is permitted to solidify while in contact with the membrane, the latter may be damaged. The improvement permits such batteries to be prefilled with catholyte and shipped, at ordinary temperatures.

  12. Superconductivity in alkali metal fullerides

    NASA Astrophysics Data System (ADS)

    Murphy, D. W.; Rosseinsky, M. J.; Haddon, R. C.; Ramirez, A. P.; Hebard, A. F.; Tycko, R.; Fleming, R. M.; Dabbagh, G.

    1991-12-01

    The recent synthesis of macroscopic quantities of spherical molecular carbon compounds, commonly called fullerenes, has stimulated a wide variety of studies of the chemical and physical properties of this novel class of compounds. We discovered that the smallest of the known fullerenes, C 60, could be made conducting and superconducting by reaction with alkali metals. In this paper, an overview of the motivation for these discoveries and some recent results are presented.

  13. The cubyl cation rearrangements.

    PubMed

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

    2016-02-25

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

  14. A second component of the SltA-dependent cation tolerance pathway in Aspergillus nidulans.

    PubMed

    Mellado, Laura; Calcagno-Pizarelli, Ana Maria; Lockington, Robin A; Cortese, Marc S; Kelly, Joan M; Arst, Herbert N; Espeso, Eduardo A

    2015-09-01

    The transcriptional response to alkali metal cation stress is mediated by the zinc finger transcription factor SltA in Aspergillus nidulans and probably in other fungi of the pezizomycotina subphylum. A second component of this pathway has been identified and characterized. SltB is a 1272 amino acid protein with at least two putative functional domains, a pseudo-kinase and a serine-endoprotease, involved in signaling to the transcription factor SltA. Absence of SltB activity results in nearly identical phenotypes to those observed for a null sltA mutant. Hypersensitivity to a variety of monovalent and divalent cations, and to medium alkalinization are among the phenotypes exhibited by a null sltB mutant. Calcium homeostasis is an exception and this cation improves growth of sltΔ mutants. Moreover, loss of kinase HalA in conjunction with loss-of-function sltA or sltB mutations leads to pronounced calcium auxotrophy. sltA sltB double null mutants display a cation stress sensitive phenotype indistinguishable from that of single slt mutants showing the close functional relationship between these two proteins. This functional relationship is reinforced by the fact that numerous mutations in both slt loci can be isolated as suppressors of poor colonial growth resulting from certain null vps (vacuolar protein sorting) mutations. In addition to allowing identification of sltB, our sltB missense mutations enabled prediction of functional regions in the SltB protein. Although the relationship between the Slt and Vps pathways remains enigmatic, absence of SltB, like that of SltA, leads to vacuolar hypertrophy. Importantly, the phenotypes of selected sltA and sltB mutations demonstrate that suppression of null vps mutations is not dependent on the inability to tolerate cation stress. Thus a specific role for both SltA and SltB in the VPS pathway seems likely. Finally, it is noteworthy that SltA and SltB have a similar, limited phylogenetic distribution, being restricted to

  15. Regenerable activated bauxite adsorbent alkali monitor probe

    DOEpatents

    Lee, Sheldon H. D.

    1992-01-01

    A regenerable activated bauxite adsorber alkali monitor probe for field applications to provide reliable measurement of alkali-vapor concentration in combustion gas with special emphasis on pressurized fluidized-bed combustion (PFBC) off-gas. More particularly, the invention relates to the development of a easily regenerable bauxite adsorbent for use in a method to accurately determine the alkali-vapor content of PFBC exhaust gases.

  16. Regenerable activated bauxite adsorbent alkali monitor probe

    DOEpatents

    Lee, S.H.D.

    1992-12-22

    A regenerable activated bauxite adsorber alkali monitor probe for field applications to provide reliable measurement of alkali-vapor concentration in combustion gas with special emphasis on pressurized fluidized-bed combustion (PFBC) off-gas. More particularly, the invention relates to the development of a easily regenerable bauxite adsorbent for use in a method to accurately determine the alkali-vapor content of PFBC exhaust gases. 6 figs.

  17. From T2,2@Bmmim to Alkali@T2,2@Bmmim Ivory Ball-like Clusters: Ionothermal Syntheses, Precise Doping, and Photocatalytic Properties.

    PubMed

    Du, Cheng-Feng; Li, Jian-Rong; Zhang, Bo; Shen, Nan-Nan; Huang, Xiao-Ying

    2015-06-15

    Presented here are the syntheses, structures, and properties of an In-Sn-Se compound based on a ternary super-supertetrahedral T2,2 cluster nested by Bmmim cations and two of its alkali-doped quaternary analogues. By means of a one-pot ionothermal method, an alkali metal ion (Cs(+) or Rb(+)) could be precisely doped into the central cavity of the cluster, forming an alkali@T2,2@Bmmim quaternary cluster. Remarkably, the undoped compound exhibited excellent stability and visible light photodegradation ability over a wide range of pH, especially in acidic conditions. PMID:26034842

  18. 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

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

    DOE PAGESBeta

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

    2016-01-21

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

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

    PubMed

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

    2016-03-01

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

  1. The interactions of sorbates with gallosilicates and alkali-metal exchanged gallosilicates

    NASA Astrophysics Data System (ADS)

    Limtrakul, J.; Kuno, M.; Treesukol, P.

    1999-11-01

    Structures, energetics and vibrational frequencies of the interaction of adsorbates with H-aluminosilicates (H-AlZ), H-gallosilicates (H-GaZ), alkali-metal exchanged aluminosilicates (X-AlZ) and alkali-metal exchanged gallosilicates (X-GaZ), where X being Li, Na, or K, have been carried out at B3LYP and HF levels of theory with 6-31G(d) as the basis set. The charge compensating alkali-metal ions can affect the catalytically active site (Si-O-T where T=Al or Ga) by weakening the Si-O, Al-O, and Ga-O bonds as compared to their anionic frameworks. Comparing the net stabilization energies, Δ ENSE, of the naked alkali-metal/H 2O adducts with those of the alkali-metal exchanged zeolite/H 2O systems, the latter amounts only to about 50% of the former, which is partly due to the destabilizing role of the negative zeolitic oxygen frameworks surrounding the cations. The interaction of sorbates with the alkali-metal exchanged gallosilicates can be employed to probe the field strength inside the catalytic frameworks as indicated by the plot of the binding energy, Δ E, versus 1/ RX-O w2, with R(X-O w) being the distance between the cationic nucleus and the oxygen atom of the adsorbate. The IR spectra of H 2O adsorbed on Na-AlZ are calculated to be 3584, 3651, and 1686 cm -1. The obtained results are in excellent agreement with the very recent experimental IR spectra of water adsorbed on Na-ZSM-5 of Zecchina et al. (J. Phys. Chem., 100 (1996) 16 484). Other important features, i.e. the correlation between Δ νOH and, Δ E, R(X-O w) , and 1/ RX-O w2, cationic size, demonstrate that the interactions of sorbates with alkali-metal exchanged gallosilicates are well approximated by electrostatic contribution.

  2. Alkali-Metal Spin Maser.

    PubMed

    Chalupczak, W; Josephs-Franks, P

    2015-07-17

    Quantum measurement is a combination of a read-out and a perturbation of the quantum system. We explore the nonlinear spin dynamics generated by a linearly polarized probe beam in a continuous measurement of the collective spin state in a thermal alkali-metal atomic sample. We demonstrate that the probe-beam-driven perturbation leads, in the presence of indirect pumping, to complete polarization of the sample and macroscopic coherent spin oscillations. As a consequence of the former we report observation of spectral profiles free from collisional broadening. Nonlinear dynamics is studied through exploring its effect on radio frequency as well as spin noise spectra. PMID:26230788

  3. Properties and Performance of Alkali-Activated Concrete

    NASA Astrophysics Data System (ADS)

    Thomas, Robert J.

    Alkali-activated concrete (AAC) made with industrial byproducts as the sole binder is rapidly emerging as a sustainable alternative to ordinary portland cement concrete (PCC). Despite its exemplary mechanical performance and durability, there remain several barriers to widespread commercialization of AAC. This dissertation addresses several of these barriers. Mathematical models are proposed which efficiently and accurately predict the compressive strength of AAC as a function of activator composition, binder type, and curing condition. The relationships between compressive strength and other mechanical properties (i.e., tensile strength and modulus of elasticity) are discussed, as are stress-strain relationships. Several aspects related to the durability of AAC are also discussed, including dimensional stability under drying conditions, alkali-silica reactivity, and chloride permeability. The results of these experimental investigations are disseminated in the context of real-world applicability.

  4. Maleic acid-styrene encapsulated silica cation exchanger in high performance liquid chromatography.

    PubMed

    Yang, R; Jiang, S; Chen, L

    2001-12-24

    The use of poly(maleic acid-styrene)-encapsulated silica for the determination of monovalent and divalent cations is well accepted in ion chromatography. The separation of Mn(2+), alkali and alkaline earth metal cations is obtained under the same chromatographic conditions. The influences of pH and the concentration of eluent on the retention of cations have been studied. The preparation conditions of packings were studied. The metal ions in the boiler water samples from a thermal power plant were quantitatively determined using this column. The results are in agreement with those determined by ICP and Volumetric analysis methods. PMID:18968461

  5. Content and Access Remain Key

    ERIC Educational Resources Information Center

    Johnson, Linda B.

    2007-01-01

    It is impossible to review the year's outstanding government publication landscape without acknowledging that change remains paramount. Just as striking, however, is that these changes go hand in hand with some familiar constants. Within this shifting environment, there are the consistency and dependability of government information itself,…

  6. An Alkali Metal-Capped Cerium(IV) Imido Complex.

    PubMed

    Solola, Lukman A; Zabula, Alexander V; Dorfner, Walter L; Manor, Brian C; Carroll, Patrick J; Schelter, Eric J

    2016-06-01

    Structurally authenticated, terminal lanthanide-ligand multiple bonds are rare and expected to be highly reactive. Even capped with an alkali metal cation, poor orbital energy matching and overlap of metal and ligand valence orbitals should result in strong charge polarization within such bonds. We expand on a new strategy for isolating terminal lanthanide-ligand multiple bonds using cerium(IV) complexes. In the current case, our tailored tris(hydroxylaminato) ligand framework, TriNOx(3-), provides steric protection against ligand scrambling and metal complex oligomerization and electronic protection against reduction. This strategy culminates in isolation of the first formal Ce═N bonded moiety in the complex [K(DME)2][Ce═N(3,5-(CF3)2C6H3)(TriNOx)], whose Ce═N bond is the shortest known at 2.119(3) Å. PMID:27163651

  7. 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

  8. Process for the disposal of alkali metals

    DOEpatents

    Lewis, Leroy C.

    1977-01-01

    Large quantities of alkali metals may be safely reacted for ultimate disposal by contact with a hot concentrated caustic solution. The alkali metals react with water in the caustic solution in a controlled reaction while steam dilutes the hydrogen formed by the reaction to a safe level.

  9. Role of encapsulated metal cation in the reactivity and regioselectivity of the C₆₀ Diels-Alder reaction.

    PubMed

    Cui, Cheng-Xing; Liu, Ya-Jun

    2015-03-26

    Endohedral metallofullerene has novel properties because of the interaction between the encapsulated metal atom or cation and fullerene. Experiments have demonstrated that the insertion of Li(+) into C60 can greatly promote the reactivity of the Diels-Alder (DA) cycloaddition of cyclopentadiene (CpH) to C60. However, the reaction is sufficiently fast that its quantitative kinetic data cannot be obtained experimentally. In addition, knowledge regarding the effects of other alkali metal cations and metal cations with more charges on the reactivity and regioselectivity of C60 is almost nonexistent. In the current study, DA cycloadditions of CpH to M(+)@C60 (where M = Li, Na, K, Rb, and Cs) and Ca(2+)@C60 were investigated via density functional theory in the gas phase and in solvent. Via careful discussion and comparison with the results of C60, we concluded the following for the DA reaction of CpH to C60 and, more generally, for DA reactions of other fullerenes: (1) the encapsulated metal cations enhance the reactivity; (2) among alkali metal cations, Na(+) could be the best catalyst; (3) Ca(2+) is more favorable in promoting the reactivity than any alkali metal cation; (4) encapsulated metal cations with more positive charges enhance the reactivity of the 6-5 bond in C60, which is significant when the 6-5 adduct is the target product. PMID:25714730

  10. Crystal chemistry of hydrothermally grown ternary alkali rare earth fluorides.

    PubMed

    McMillen, Colin D; Comer, Sara; Fulle, Kyle; Sanjeewa, Liurukara D; Kolis, Joseph W

    2015-12-01

    The structural variations of several alkali metal rare earth fluoride single crystals are summarized. Two different stoichiometric formulations are considered, namely those of ARE2F7 and ARE3F10 (A = K, Rb, Cs; RE = Y, La-Lu), over a wide range of ionic radii of both the alkali and rare earth (RE) ions. Previously reported and several new single-crystal structures are considered. The new single crystals are grown using hydrothermal methods and the structures are compared with literature reports of structures grown from both melts and hydrothermal fluids. The data reported here are combined with the literature data to gain a greater understanding of structural subtleties surrounding these systems. The work underscores the importance of the size of the cations to the observed structure type and also introduces synthetic technique as a contributor to the same. New insights based on single-crystal structure analysis in the work introduce a new disordered structure type in the case of ARE2F7, and examine the trends and boundaries of the ARE3F10 stoichiometry. Such fundamental structural information is useful in understanding the potential applications of these compounds as optical materials. PMID:26634734

  11. Cationic Lipid-Based Nucleic Acid Vectors.

    PubMed

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

    2016-01-01

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

  12. Electronic excitation in bulk and nanocrystalline alkali halides.

    PubMed

    Bichoutskaia, Elena; Pyper, Nicholas C

    2012-11-14

    The lowest energy excitations in bulk alkali halides are investigated by considering five different excited state descriptions. It is concluded that excitation transfers one outermost halide electron in the fully ionic ground state to the lowest energy vacant s orbital of one closest cation neighbour to produce the excited state termed dipolar. The excitation energies of seven salts were computed using shell model description of the lattice polarization produced by the effective dipole moment of the excited state neutral halogen-neutral metal pair. Ab initio uncorrelated short-range inter-ionic interactions computed from anion wavefunctions adapted to the in-crystal environment were augmented by short-range electron correlation contributions derived from uniform electron-gas density functional theory. Dispersive attractions including wavefunction overlap damping were introduced using reliable semi-empirical dispersion coefficients. The good agreement between the predicted excitation energies and experiment provides strong evidence that the excited state is dipolar. In alkali halide nanocrystals in which each ionic plane contains only four ions, the Madelung energies are significantly reduced compared with the bulk. This predicts that the corresponding intra-crystal excitation energies in the nanocrystals, where there are two excited states depending on whether the halide electron is transferred to a cation in the same or in the neighbouring plane, will be reduced by almost 2 eV. For such an encapsulated KI crystal, it has been shown that the greater polarization in the excited state of the bulk crystal causes these reductions to be lowered to a 1.1 eV-1.5 eV range for the case of charge transfer to a neighbouring plane. For intra-plane charge transfer the magnitude of the polarization energy is further reduced thus causing the excitation in these encapsulated materials to be only 0.2 eV less than in the bulk crystal. PMID:23163361

  13. Method of handling radioactive alkali metal waste

    DOEpatents

    Wolson, Raymond D.; McPheeters, Charles C.

    1980-01-01

    Radioactive alkali metal is mixed with particulate silica in a rotary drum reactor in which the alkali metal is converted to the monoxide during rotation of the reactor to produce particulate silica coated with the alkali metal monoxide suitable as a feed material to make a glass for storing radioactive material. Silica particles, the majority of which pass through a 95 mesh screen or preferably through a 200 mesh screen, are employed in this process, and the preferred weight ratio of silica to alkali metal is 7 to 1 in order to produce a feed material for the final glass product having a silica to alkali metal monoxide ratio of about 5 to 1.

  14. Method of handling radioactive alkali metal waste

    DOEpatents

    Wolson, R.D.; McPheeters, C.C.

    Radioactive alkali metal is mixed with particulate silica in a rotary drum reactor in which the alkali metal is converted to the monoxide during rotation of the reactor to produce particulate silica coated with the alkali metal monoxide suitable as a feed material to make a glass for storing radioactive material. Silica particles, the majority of which pass through a 95 mesh screen or preferably through a 200 mesh screen, are employed in this process, and the preferred weight ratio of silica to alkali metal is 7 to 1 in order to produce a feed material for the final glass product having a silica to alkali metal monoxide ratio of about 5 to 1.

  15. Lattice strain across Na-K interdiffusion fronts in alkali feldspar: an electron back-scatter diffraction study

    NASA Astrophysics Data System (ADS)

    Schäffer, Anne-Kathrin; Jäpel, Tom; Zaefferer, Stefan; Abart, Rainer; Rhede, Dieter

    2014-11-01

    Cation exchange experiments between gem quality sanidine and KCl melt produced chemical alteration of alkali feldspar starting at the grain surface and propagating inwards by highly anisotropic Na-K interdiffusion on the alkali sublattice. Diffusion fronts developing in b-direction are very sharp, while diffusion fronts within the a- c-plane are comparatively broad. Due to the composition dependence of the lattice parameters of alkali feldspar, the diffusion induced compositional heterogeneity induces coherency stress and elastic strain. Electron back-scatter diffraction combined with the cross-correlation technique was employed to determine the lattice strain distribution across the Na-K interdiffusion fronts in partially exchanged single crystals of alkali feldspar. The strain changes gradually across the broad fronts within the a- c-plane, with a successive extension primarily in a-direction conferring to the composition strain in unstressed alkali feldspar. In contrast, lattice strain characterised by pronounced extension in b-direction is localised at the sharp diffusion fronts parallel to b, followed by a slight expansion in a-direction in the orthoclase-rich rim. This strain pattern does not confer with the composition induced lattice strain in a stress-free alkali feldspar. It may rather be explained by the mechanical coupling of the exchanged surface layer and the mechanically strong substratum. The lattice distortion localised at the sharp diffusion front may have an influence on the diffusion process and appears to produce a self-sharpening feedback, leading to a local reduction of component mobilities.

  16. Alkali burns from wet cement.

    PubMed Central

    Peters, W. J.

    1984-01-01

    When water is added to the dry materials of Portland cement calcium hydroxide is formed; the wet cement is caustic (with a pH as high as 12.9) and can produce third-degree alkali burns after 2 hours of contact. Unlike professional cement workers, amateurs are usually not aware of any danger and may stand or kneel in the cement for long periods. As illustrated in a case report, general physicians may recognize neither the seriousness of the injury in its early stages nor the significance of a history of prolonged contact with wet cement. All people working with cement should be warned about its dangers and advised to immediately wash and dry the skin if contact does occur. Images Fig. 1 PMID:6561052

  17. Integrating Sphere Alkali-Metal Vapor Cells

    NASA Astrophysics Data System (ADS)

    McGuyer, Bart; Ben-Kish, Amit; Jau, Yuan-Yu; Happer, William

    2010-03-01

    An integrating sphere is an optical multi-pass cavity that uses diffuse reflection to increase the optical path length. Typically applied in photometry and radiometry, integrating spheres have previously been used to detect trace gases and to cool and trap alkali-metal atoms. Here, we investigate the potential for integrating spheres to enhance optical absorption in optically thin alkali-metal vapor cells. In particular, we consider the importance of dielectric effects due to a glass container for the alkali-metal vapor. Potential applications include miniature atomic clocks and magnetometers, where multi-passing could reduce the operating temperature and power consumption.

  18. Alkali Silicate Vehicle Forms Durable, Fireproof Paint

    NASA Technical Reports Server (NTRS)

    Schutt, John B.; Seindenberg, Benjamin

    1964-01-01

    The problem: To develop a paint for use on satellites or space vehicles that exhibits high resistance to cracking, peeling, or flaking when subjected to a wide range of temperatures. Organic coatings will partially meet the required specifications but have the inherent disadvantage of combustibility. Alkali-silicate binders, used in some industrial coatings and adhesives, show evidence of forming a fireproof paint, but the problem of high surface-tension, a characteristic of alkali silicates, has not been resolved. The solution: Use of a suitable non-ionic wetting agent combined with a paint incorporating alkali silicate as the binder.

  19. Diode pumped alkali vapor fiber laser

    DOEpatents

    Payne, Stephen A.; Beach, Raymond J.; Dawson, Jay W.; Krupke, William F.

    2007-10-23

    A method and apparatus is provided for producing near-diffraction-limited laser light, or amplifying near-diffraction-limited light, in diode pumped alkali vapor photonic-band-gap fiber lasers or amplifiers. Laser light is both substantially generated and propagated in an alkali gas instead of a solid, allowing the nonlinear and damage limitations of conventional solid core fibers to be circumvented. Alkali vapor is introduced into the center hole of a photonic-band-gap fiber, which can then be pumped with light from a pump laser and operated as an oscillator with a seed beam, or can be configured as an amplifier.

  20. Diode pumped alkali vapor fiber laser

    DOEpatents

    Payne, Stephen A.; Beach, Raymond J.; Dawson, Jay W.; Krupke, William F.

    2006-07-26

    A method and apparatus is provided for producing near-diffraction-limited laser light, or amplifying near-diffraction-limited light, in diode pumped alkali vapor photonic-band-gap fiber lasers or amplifiers. Laser light is both substantially generated and propagated in an alkali gas instead of a solid, allowing the nonlinear and damage limitations of conventional solid core fibers to be circumvented. Alkali vapor is introduced into the center hole of a photonic-band-gap fiber, which can then be pumped with light from a pump laser and operated as an oscillator with a seed beam, or can be configured as an amplifier.

  1. Advancements in flowing diode pumped alkali lasers

    NASA Astrophysics Data System (ADS)

    Pitz, Greg A.; Stalnaker, Donald M.; Guild, Eric M.; Oliker, Benjamin Q.; Moran, Paul J.; Townsend, Steven W.; Hostutler, David A.

    2016-03-01

    Multiple variants of the Diode Pumped Alkali Laser (DPAL) have recently been demonstrated at the Air Force Research Laboratory (AFRL). Highlights of this ongoing research effort include: a) a 571W rubidium (Rb) based Master Oscillator Power Amplifier (MOPA) with a gain (2α) of 0.48 cm-1, b) a rubidium-cesium (Cs) Multi-Alkali Multi-Line (MAML) laser that simultaneously lases at both 795 nm and 895 nm, and c) a 1.5 kW resonantly pumped potassium (K) DPAL with a slope efficiency of 50%. The common factor among these experiments is the use of a flowing alkali test bed.

  2. Theoretical and experimental investigation of force imaging at the atomic scale on alkali halide crystals

    NASA Astrophysics Data System (ADS)

    Shluger, A. L.; Wilson, R. Mark; Williams, R. T.

    1994-02-01

    Assuming a model tip (Si4O10H10) as a reasonable representation of the surface of a Si3N4 cantilever stylus having a hydrogen-terminated asperity and a broader load-bearing base, we investigate the interaction of an atomic force microscope (AFM) with an alkali halide crystal by quantum chemical methods. Structural relaxation of the sample during engagement is allowed, and defect formation is investigated. Force curves above cation and anion positions are calculated, determining maximum sustainable loads and indicating a basis for atomic contrast. Experiments using a Si3N4 cantilever for AFM imaging of 12 alkali halide and alkaline earth fluoride crystals in air and desiccated helium are reported, in the widest AFM survey of such materials to date. Adsorbed water is shown to significantly enhance the observation of atomic periodicity on ionic halide samples, and rapid surface diffusion on alkali halide crystals is illustrated as it affects prospects for defect investigations. Observations of step edges and point-defect candidates at atomic scale are reported. The theoretical and experimental results are discussed together in the effort to provide a quantum-mechanical model for observations of alkali halide samples at atomic resolution, and to examine a possible basis for atomic resolution in the presence of long-range attractive forces.

  3. Alkali metal for ultraviolet band-pass filter

    NASA Technical Reports Server (NTRS)

    Mardesich, Nick (Inventor); Fraschetti, George A. (Inventor); Mccann, Timothy A. (Inventor); Mayall, Sherwood D. (Inventor); Dunn, Donald E. (Inventor); Trauger, John T. (Inventor)

    1993-01-01

    An alkali metal filter having a layer of metallic bismuth deposited onto the alkali metal is provided. The metallic bismuth acts to stabilize the surface of the alkali metal to prevent substantial surface migration from occurring on the alkali metal, which may degrade optical characteristics of the filter. To this end, a layer of metallic bismuth is deposited by vapor deposition over the alkali metal to a depth of approximately 5 to 10 A. A complete alkali metal filter is described along with a method for fabricating the alkali metal filter.

  4. Intrinsic Impurities in Glass Alkali-Vapor Cells

    NASA Astrophysics Data System (ADS)

    Patton, B.; Ishikawa, K.; Jau, Y.-Y.; Happer, W.

    2007-07-01

    We report NMR measurements of metallic Cs133 in glass cells. The solid-liquid phase transition was studied by observing the NMR peaks arising from these two phases; surprisingly, many cells yielded two additional NMR peaks below the melting point. We attribute these signals to two distinct impurities which can dissolve in the liquid alkali metal and affect its chemical shift. Intentional contamination of cesium cells with O2 confirms this hypothesis for one peak. The other contaminant remains unknown but can appear in evacuated cells. Similar effects have been seen in Rb87 cells.

  5. Silicon photonics: some remaining challenges

    NASA Astrophysics Data System (ADS)

    Reed, G. T.; Topley, R.; Khokhar, A. Z.; Thompson, D. J.; Stanković, S.; Reynolds, S.; Chen, X.; Soper, N.; Mitchell, C. J.; Hu, Y.; Shen, L.; Martinez-Jimenez, G.; Healy, N.; Mailis, S.; Peacock, A. C.; Nedeljkovic, M.; Gardes, F. Y.; Soler Penades, J.; Alonso-Ramos, C.; Ortega-Monux, A.; Wanguemert-Perez, G.; Molina-Fernandez, I.; Cheben, P.; Mashanovich, G. Z.

    2016-03-01

    This paper discusses some of the remaining challenges for silicon photonics, and how we at Southampton University have approached some of them. Despite phenomenal advances in the field of Silicon Photonics, there are a number of areas that still require development. For short to medium reach applications, there is a need to improve the power consumption of photonic circuits such that inter-chip, and perhaps intra-chip applications are viable. This means that yet smaller devices are required as well as thermally stable devices, and multiple wavelength channels. In turn this demands smaller, more efficient modulators, athermal circuits, and improved wavelength division multiplexers. The debate continues as to whether on-chip lasers are necessary for all applications, but an efficient low cost laser would benefit many applications. Multi-layer photonics offers the possibility of increasing the complexity and effectiveness of a given area of chip real estate, but it is a demanding challenge. Low cost packaging (in particular, passive alignment of fibre to waveguide), and effective wafer scale testing strategies, are also essential for mass market applications. Whilst solutions to these challenges would enhance most applications, a derivative technology is emerging, that of Mid Infra-Red (MIR) silicon photonics. This field will build on existing developments, but will require key enhancements to facilitate functionality at longer wavelengths. In common with mainstream silicon photonics, significant developments have been made, but there is still much left to do. Here we summarise some of our recent work towards wafer scale testing, passive alignment, multiplexing, and MIR silicon photonics technology.

  6. Alkali Metal Handling Practices at NASA MSFC

    NASA Technical Reports Server (NTRS)

    Salvail, Patrick G.; Carter, Robert R.

    2002-01-01

    NASA Marshall Space Flight Center (MSFC) is NASA s principle propulsion development center. Research and development is coordinated and carried out on not only the existing transportation systems, but also those that may be flown in the near future. Heat pipe cooled fast fission cores are among several concepts being considered for the Nuclear Systems Initiative. Marshall Space Flight Center has developed a capability to handle high-purity alkali metals for use in heat pipes or liquid metal heat transfer loops. This capability is a low budget prototype of an alkali metal handling system that would allow the production of flight qualified heat pipe modules or alkali metal loops. The processing approach used to introduce pure alkali metal into heat pipe modules and other test articles are described in this paper.

  7. Alkali-metal intercalation in carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Béguin, F.; Duclaux, L.; Méténier, K.; Frackowiak, E.; Salvetat, J. P.; Conard, J.; Bonnamy, S.; Lauginie, P.

    1999-09-01

    We report on successful intercalation of multiwall (MWNT) and single wall (SWNT) carbon nanotubes with alkali metals by electrochemical and vapor phase reactions. A LiC10 compound was produced by full electrochemical reduction of MWNT. KC8 and CsC8-MWNT first stage derivatives were synthesized in conditions of alkali vapor saturation. Their identity periods and the 2×2 R 0° alkali superlattice are comparable to their parent graphite compounds. The dysonian shape of KC8 EPR line and the temperature-independent Pauli susceptibility are both characteristic of a metallic behavior, which was confirmed by 13C NMR anisotropic shifts. Exposure of SWNT bundles to alkali vapor led to an increase of the pristine triangular lattice from 1.67 nm to 1.85 nm and 1.87 nm for potassium and rubidium, respectively.

  8. Alkali metal intercalates of molybdenum disulfide.

    NASA Technical Reports Server (NTRS)

    Somoano, R. B.; Hadek, V.; Rembaum, A.

    1973-01-01

    Study of some of the physicochemical properties of compounds obtained by subjecting natural molybdenite and single crystals of molybdenum disulfide grown by chemical vapor transport to intercalation with the alkali group of metals (Li, Na, K, Rb, and Cs) by means of the liquid ammonia technique. Reported data and results include: (1) the intercalation of the entire alkali metal group, (2) stoichiometries and X-ray data on all of the compounds, and (3) superconductivity data for all the intercalation compounds.

  9. Superconductivity in alkali-doped C60

    NASA Astrophysics Data System (ADS)

    Ramirez, Arthur P.

    2015-07-01

    Superconductivity in alkali-doped C60 (A3C60, A = an alkali atom) is well described by an s-wave state produced by phonon mediated pairing. Moderate coupling of electrons to high-frequency shape-changing intra-molecular vibrational modes produces transition temperatures (Tc) up to 33 K in single-phase material. The good understanding of pairing in A3C60 offers a paradigm for the development of new superconducting materials.

  10. Desulfurizing Coal With an Alkali Treatment

    NASA Technical Reports Server (NTRS)

    Ravindram, M.; Kalvinskas, J. J.

    1987-01-01

    Experimental coal-desulfurization process uses alkalies and steam in fluidized-bed reactor. With highly volatile, high-sulfur bituminous coal, process removed 98 percent of pyritic sulfur and 47 percent of organic sulfur. Used in coal liquefaction and in production of clean solid fuels and synthetic liquid fuels. Nitrogen or steam flows through bed of coal in reactor. Alkalies react with sulfur, removing it from coal. Nitrogen flow fluidizes bed while heating or cooling; steam is fluidizing medium during reaction.

  11. Alkali metal crystalline polymer electrolytes.

    PubMed

    Zhang, Chuhong; Gamble, Stephen; Ainsworth, David; Slawin, Alexandra M Z; Andreev, Yuri G; Bruce, Peter G

    2009-07-01

    Polymer electrolytes have been studied extensively because uniquely they combine ionic conductivity with solid yet flexible mechanical properties, rendering them important for all-solid-state devices including batteries, electrochromic displays and smart windows. For some 30 years, ionic conductivity in polymers was considered to occur only in the amorphous state above Tg. Crystalline polymers were believed to be insulators. This changed with the discovery of Li(+) conductivity in crystalline poly(ethylene oxide)(6):LiAsF(6). However, new crystalline polymer electrolytes have proved elusive, questioning whether the 6:1 complex has particular structural features making it a unique exception to the rule that only amorphous polymers conduct. Here, we demonstrate that ionic conductivity in crystalline polymers is not unique to the 6:1 complex by reporting several new crystalline polymer electrolytes containing different alkali metal salts (Na(+), K(+) and Rb(+)), including the best conductor poly(ethylene oxide)(8):NaAsF(6) discovered so far, with a conductivity 1.5 orders of magnitude higher than poly(ethylene oxide)(6):LiAsF(6). These are the first crystalline polymer electrolytes with a different composition and structures to that of the 6:1 Li(+) complex. PMID:19543313

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

    PubMed Central

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

    2013-01-01

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

  13. Theory of magic optical traps for Zeeman-insensitive clock transitions in alkali-metal atoms

    SciTech Connect

    Derevianko, Andrei

    2010-05-15

    Precision measurements and quantum-information processing with cold atoms may benefit from trapping atoms with specially engineered, 'magic' optical fields. At the magic trapping conditions, the relevant atomic properties remain immune to strong perturbations by the trapping fields. Here we develop a theoretical analysis of magic trapping for especially valuable Zeeman-insensitive clock transitions in alkali-metal atoms. The involved mechanism relies on applying a magic bias B field along a circularly polarized trapping laser field. We map out these B fields as a function of trapping laser wavelength for all commonly used alkalis. We also highlight a common error in evaluating Stark shifts of hyperfine manifolds.

  14. Changes in the elastic moduli of C-S-H due to presence of interlaminar cations

    NASA Astrophysics Data System (ADS)

    Mejia, Shirley; Hoyos, Bibian

    2016-03-01

    A set of models of calcium silicate hydrate (C-S-H) with alkali cations in the interlaminar layer, various calcium/silicon ratios, and each with a density of 2.4 g cm-3 is presented. Using molecular simulation techniques, the objective was to study how the Young’s, bulk, and shear modulus, as well as the Poisson’s ratio changed due to the presence of monovalent ions. The effect of density on the elastic moduli was neglected, thus the NVT ensemble was used. Comparing the different simulation cells, it was found that models with sodium and potassium ions in the structure and an alkali/silicon ratio of 0.18 showed negative effects on the elastic moduli of C-S-H. This could be mainly ascribed to the shielding effect of the alkali on the interlaminar interactions that contribute to the cohesion between the layers of C-S-H.

  15. Oxygen-consuming chlor alkali cell configured to minimize peroxide formation

    DOEpatents

    Chlistunoff, Jerzy B.; Lipp, Ludwig; Gottesfeld, Shimshon

    2006-08-01

    Oxygen-consuming zero gap chlor-alkali cell was configured to minimize peroxide formation. The cell included an ion-exchange membrane that divided the cell into an anode chamber including an anode and a cathode chamber including an oxygen gas diffusion cathode. The cathode included a single-piece of electrically conducting graphitized carbon cloth. Catalyst and polytetrafluoroethylene were attached to only one side of the cloth. When the cathode was positioned against the cation exchange membrane with the catalyst side away from the membrane, electrolysis of sodium chloride to chlorine and caustic (sodium hydroxide) proceeded with minimal peroxide formation.

  16. Coordination of trivalent metal cations to peptides: results from IRMPD spectroscopy and theory.

    PubMed

    Prell, James S; Flick, Tawnya G; Oomens, Jos; Berden, Giel; Williams, Evan R

    2010-01-21

    Structures of trivalent lanthanide metal cations La(3+), Ho(3+), and Eu(3+) with deprotonated Ala(n) (n = 2-5) or Leu-enk (Tyr-Gly-Gly-Phe-Leu) are investigated with infrared multiple photon dissociation (IRMPD) spectroscopy between 900 and 1850 cm(-1) and theory. In all of these complexes, a salt bridge is formed in which the metal cation coordinates to the carboxylate group of the peptide, resulting in a limited conformational space and many sharp IRMPD spectral bands. The IRMPD spectra clearly indicate that all carbonyl groups solvate the metal cation in each of the Ala(n) complexes. Due to strong vibrational coupling between the carbonyl groups, a sharp, high-energy amide I band due to in-phase stretching of all of the amide carbonyl groups bound to the metal cation is observed that is separated by approximately 50 cm(-1) from a strong, lower-energy amide I band. This extent of carbonyl coupling, which is sometimes observed in condensed-phase peptide and protein IR spectroscopy, has not been reported in IRMPD spectroscopy studies of other cationized peptide complexes. Intense bands due to carbonyl groups not associated with the metal cation are observed for Leu-enk complexes, indicating that a side chain group, such as the Tyr or Phe aromatic ring, prevents complete carbonyl coordination of the metal cation. Substitution of smaller lanthanide cations for La(3+) in these peptide complexes results only in minor structural changes consistent with the change in metal cation size. These are the first IRMPD spectra reported for lanthanide metal cationized peptides, and comparison to previously reported protonated and alkali metal or alkaline earth metal cationized peptide complexes reveals many trends consistent with the higher charge state of the lanthanide cations. PMID:19950916

  17. Complex formation of alkaline-earth cations with crown ethers and cryptands in methanol solutions

    SciTech Connect

    Buschman, H.J.

    1986-06-01

    The complexation of alkaline-earth cations by different crown ethers, azacrown ethers, and cryptands has been studied in methanol solutions by means of calorimetric and potentiometric titrations. The smallest monocyclic ligands examined from 2:1 complexes (ratio of ligand to cation) with cations which are too large to fit into the ligand cavity. With the smallest cryptand, only Sr/sup 2 +/ and Ba/sup 2 +/ ions are able to form exclusive complexes. In the case of the reaction of cryptand (211) with Ca/sup 2 +/, a separate estimation of stability constants for the formation of exclusive and inclusive complexes was possible for the first time. Higher values for stability constants are found for the reaction of alkaline-earth cations with cryptands compared to the reaction with alkali ions. This increase is only caused by favorable entropic contributions.

  18. Force Fields for Carbohydrate-Divalent Cation Interactions.

    PubMed

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

    2016-06-16

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

  19. Crystal Structures of Three Framework Alkali Metal Uranyl Phosphate Hydrates

    NASA Astrophysics Data System (ADS)

    Locock, Andrew J.; Burns, Peter C.

    2002-08-01

    Three homeotypic hydrated alkali metal uranyl phosphates, A2(UO 2)[(UO 2)(PO 4)] 4(H 2O) 2, A=Cs ( CsUP), Rb ( RbUP), K ( KUP), were synthesized by hydrothermal methods. Intensity data were collected at room temperature using Mo Kα radiation and a CCD-based area detector. Their crystal structures were solved by Patterson ( CsUP) and direct ( RbUP, KUP) methods and refined by full-matrix least-squares techniques to agreement indices ( CsUP, RbUP, KUP) w R2=0.048, 0.230, 0.072 for all data, and R1=0.023, 0.078, 0.038 calculated for 5338, 4738, 4514 unique observed reflections (∣ Fo∣≥4 σF), respectively. The compound CsUP is orthorhombic, space group Cmc2 1, Z=4, a=14.854(1), b=13.879(1), c=12.987(1) Å, V=2677.5(3) Å 3. Both RbUP and KUP are monoclinic, space group Cm, but are presented in the unconventional pseudo-orthorhombic space group Fm11 to facilitate comparison with CsUP and to allow a model for RbUP that includes the effects of pseudo-merohedral twinning. RbUP is monoclinic, space group Fm11, Z=4, a=15.72(2), b=13.84(1), c=13.05(1) Å, α=90.39°(2), V=2839(5) Å 3; KUP is monoclinic, space group Fm11, Z=4, a=15.257(1), b=13.831(1), c=13.007(1) Å, α=91.760°(1), V=2743.4(3) Å 3. The structures consist of sheets of phosphate tetrahedra and uranyl pentagonal bipyramids, with composition [(UO 2)(PO 4)] -, that are topologically identical to the uranyl silicate sheets in uranophane-beta. These sheets are connected by a uranyl pentagonal bipyramid in the interlayer that shares corners with two phosphate tetrahedra on each of two adjacent sheets and whose fifth equatorial vertex is an H 2O group, resulting in an open framework with alkali metal cations in the larger cavities of the structures. Where CsUP and RbUP have two alkali metal positions and a H 2O group in these cavities, KUP has four K atoms and two H 2O groups, all of which are partially occupied, in the interstitial sites.

  20. Cation-specific effects on enzymatic catalysis driven by interactions at the tunnel mouth.

    PubMed

    Štěpánková, Veronika; Paterová, Jana; Damborský, Jiří; Jungwirth, Pavel; Chaloupková, Radka; Heyda, Jan

    2013-05-30

    Cationic specificity which follows the Hofmeister series has been established for the catalytic efficiency of haloalkane dehalogenase LinB by a combination of molecular dynamics simulations and enzyme kinetic experiments. Simulations provided a detailed molecular picture of cation interactions with negatively charged residues on the protein surface, particularly at the tunnel mouth leading to the enzyme active site. On the basis of the binding affinities, cations were ordered as Na(+) > K(+) > Rb(+) > Cs(+). In agreement with this result, a steady-state kinetic analysis disclosed that the smaller alkali cations influence formation and productivity of enzyme-substrate complexes more efficiently than the larger ones. A subsequent systematic investigation of two LinB mutants with engineered charge in the cation-binding site revealed that the observed cation affinities are enhanced by increasing the number of negatively charged residues at the tunnel mouth, and vice versa, reduced by decreasing this number. However, the cation-specific effects are overwhelmed by strong electrostatic interactions in the former case. Interestingly, the substrate inhibition of the mutant LinB L177D in the presence of chloride salts was 7 times lower than that of LinB wild type in glycine buffer. Our work provides new insight into the mechanisms of specific cation effects on enzyme activity and suggests a potential strategy for suppression of substrate inhibition by the combination of protein and medium engineering. PMID:23627286

  1. 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. PMID:25874864

  2. Structure-Directing Behaviors of Tetraethylammonium Cations toward Zeolite Beta Revealed by the Evolution of Aluminosilicate Species Formed during the Crystallization Process.

    PubMed

    Ikuno, Takaaki; Chaikittisilp, Watcharop; Liu, Zhendong; Iida, Takayuki; Yanaba, Yutaka; Yoshikawa, Takeshi; Kohara, Shinji; Wakihara, Toru; Okubo, Tatsuya

    2015-11-18

    Organic structure-directing agents (OSDAs) have been widely used for the synthesis of zeolites. In most cases, OSDAs are occluded in zeolites as an isolated cation or molecule geometrically fitted within the zeolite cavities. This is not the case for zeolite beta synthesized by using tetraethylammonium (TEA(+)) cation as an OSDA, in which a cluster/aggregate of ca. six TEA(+) cations is occluded intact in the cavity (i.e., the channel intersection) of zeolite beta. The structure direction of TEA(+) in such a nontypical, clustered mode has remained elusive. Here, zeolite beta was hydrothermally synthesized using TEA(+) in the absence of other alkali metal cations in order to focus on the structure-directing behaviors of TEA(+) alone. The solid products formed throughout the hydrothermal synthesis were analyzed by an array of characterization techniques including argon adsorption-desorption, high-energy X-ray total scattering, Raman and solid-state NMR spectroscopy, and high-resolution transmission electron microscopy. It was revealed that the formation of amorphous TEA(+)-aluminosilicate composites and their structural, chemical, and textural evolution toward the amorphous zeolite beta-like structure during the induction period is vital for the formation of zeolite beta. A comprehensive scheme of the formation of zeolite beta is proposed paying attention to the clustered behavior of TEA(+) as follows: (i) the formation of the TEA(+)-aluminosilicate composites after heating, (ii) the reorganization of aluminosilicates together with the conformational rearrangement of TEA(+), yielding the formation of the amorphous TEA(+)-aluminosilicate composites with the zeolite beta-like structure, (iii) the formation of zeolite beta nuclei by solid-state reorganization of such zeolite beta-like, TEA(+)-aluminosilicate composites, and (iv) the subsequent crystal growth. It is anticipated that these findings can provide a basis for broadening the utilization of OSDAs in the

  3. Alkali metal adsorption on Al(111)

    NASA Astrophysics Data System (ADS)

    Andersen, J. N.; Lundgren, E.; Nyholm, R.; Qvarford, M.

    1993-06-01

    The submonolayer adsorption of Na, K, Rb, and Cs on the Al(111) surface at 100 K and at room temperature is investigated by high resolution core level spectroscopy and low energy electron diffraction. It is found that the first alkali atoms on the surface adsorb at surface defects. At higher coverages, up to approximately one third of the maximum submonolayer coverage, alkali atoms adsorbed at defects coexist with a dispersed phase. At higher coverages island formation is found to occur for the majority of the systems. It is argued that all of the ordered structures formed at room temperature involve a disruption of the Al(111) surface in contrast to the situation at 100 K where the alkali atoms adsorb as adatoms.

  4. SAFE Alkali Metal Heat Pipe Reliability

    NASA Astrophysics Data System (ADS)

    Reid, Robert S.

    2003-01-01

    Alkali metal heat pipes are among the best understood and tested of components for first generation space fission reactors. A flight reactor will require production of a hundred or more heat pipes with assured reliability over a number of years. To date, alkali metal heat pipes have been built mostly in low budget development environments with little formal quality assurance. Despite this, heat pipe test samples suggest that high reliability can be achieved with the care justified for space flight qualification. Fabrication procedures have been established that, if consistently applied, ensure long-term trouble-free heat pipe operation. Alkali metal heat pipes have been successfully flight tested in micro gravity and also have been shown capable of multi-year operation with no evidence of sensitivity to fast neutron fluence up to 1023 n/cm2. This represents 50 times the fluence of the proposed Safe Affordable Fission Engine (SAFE-100) heat pipe reactor core.

  5. Diode pumped alkali lasers (DPALs): an overview

    NASA Astrophysics Data System (ADS)

    Krupke, William F.

    2008-05-01

    The concept of power-scalable, high beam-quality diode pumped alkali lasers was introduced in 2003 [Krupke, US Patent No. 6,643,311; Opt. Letters, 28, 2336 (2003)]. Since then several laboratory DPAL devices have been reported on, confirming many of the spectroscopic, kinetic, and laser characteristics projected from literature data. This talk will present an overview of the DPAL concept, summarize key relevant properties of the cesium, rubidium, and potassium alkali vapor gain media so-far examined, outline power scaling considerations, and highlight results of published DPAL laboratory experiments.

  6. Alkali metal vapors - Laser spectroscopy and applications

    NASA Technical Reports Server (NTRS)

    Stwalley, W. C.; Koch, M. E.

    1980-01-01

    The paper examines the rapidly expanding use of lasers for spectroscopic studies of alkali metal vapors. Since the alkali metals (lithium, sodium, potassium, rubidium and cesium) are theoretically simple ('visible hydrogen'), readily ionized, and strongly interacting with laser light, they represent ideal systems for quantitative understanding of microscopic interconversion mechanisms between photon (e.g., solar or laser), chemical, electrical and thermal energy. The possible implications of such understanding for a wide variety of practical applications (sodium lamps, thermionic converters, magnetohydrodynamic devices, new lasers, 'lithium waterfall' inertial confinement fusion reactors, etc.) are also discussed.

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

    PubMed Central

    Gagné, Olivier Charles; Hawthorne, Frank Christopher

    2016-01-01

    Bond-length distributions have been examined for 55 configurations of alkali-metal ions and 29 configurations of alkaline-earth-metal ions bonded to oxygen, for 4859 coordination polyhedra and 38 594 bond distances (alkali metals), and for 3038 coordination polyhedra and 24 487 bond distances (alkaline-earth metals). Bond lengths generally show a positively skewed Gaussian distribution that originates from the variation in Born repulsion and Coulomb attraction as a function of interatomic distance. The skewness and kurtosis of these distributions generally decrease with increasing coordination number of the central cation, a result of decreasing Born repulsion with increasing coordination number. We confirm the following minimum coordination numbers: [3]Li+, [3]Na+, [4]K+, [4]Rb+, [6]Cs+, [3]Be2+, [4]Mg2+, [6]Ca2+, [6]Sr2+ and [6]Ba2+, but note that some reported examples are the result of extensive dynamic and/or positional short-range disorder and are not ordered arrangements. Some distributions of bond lengths are distinctly multi-modal. This is commonly due to the occurrence of large numbers of structure refinements of a particular structure type in which a particular cation is always present, leading to an over-representation of a specific range of bond lengths. Outliers in the distributions of mean bond lengths are often associated with anomalous values of atomic displacement of the constituent cations and/or anions. For a sample of [6]Na+, the ratio U eq(Na)/U eq(bonded anions) is partially correlated with 〈[6]Na+—O2−〉 (R 2 = 0.57), suggesting that the mean bond length is correlated with vibrational/displacement characteristics of the constituent ions for a fixed coordination number. Mean bond lengths also show a weak correlation with bond-length distortion from the mean value in general, although some coordination numbers show the widest variation in mean bond length for zero distortion, e.g. Li+ in [4]- and [6]-coordination, Na+ in [4]- and [6

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

    PubMed

    Gagné, Olivier Charles; Hawthorne, Frank Christopher

    2016-08-01

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

  9. Alkali-aggregate reaction in concrete containing high-alkali cement and granite aggregate

    SciTech Connect

    Owsiak, Z

    2004-01-01

    The paper discusses results of the research into the influence of high-alkali Portland cement on granite aggregate. The deformation of the concrete structure occurred after 18 months. The research was carried out by means of a scanning electron microscope equipped with a high-energy dispersive X-ray analyzer that allowed observation of unpolished sections of concrete bars exhibiting the cracking pattern typical of the alkali-silica reaction. Both the microscopic observation and the X-ray elemental analysis confirm the presence of alkali-silica gel and secondary ettringite in the cracks.

  10. Recovery of alkali metal constituents from catalytic coal conversion residues

    DOEpatents

    Soung, W.Y.

    In a coal gasification operation (32) or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by contacting them with water or an aqueous solution to remove water-soluble alkali metal constituents and produce an aqueous solution enriched in said constituents. The aqueous solution thus produced is then contacted with carbon dioxide to precipitate silicon constituents, the pH of the resultant solution is increased, preferably to a value in the range between about 12.5 and about 15.0, and the solution of increased pH is evaporated to increase the alkali metal concentration. The concentrated aqueous solution is then recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

  11. Surface charge density on silica in alkali and alkaline earth chloride electrolyte solutions

    NASA Astrophysics Data System (ADS)

    Dove, Patricia M.; Craven, Colin M.

    2005-11-01

    The surface charge density of colloidal SiO 2 (Aerosil 380) was measured in alkali chloride (0.067 and 0.20 M LiCl, NaCl, and KCl) and alkaline earth chloride (0.067 M MgCl 2, CaCl 2, SrCl 2, BaCl 2) solutions. Measurements were conducted at 25°C by potentiometric titrations using the constant ionic medium method in a CO 2-free system. The experimental design measured surface charge for solutions with constant ionic strength as well as constant cation concentration. Alkali chloride solutions promote negative surface charge density in the order LiCl < NaCl < KCl to give the "regular" lyotropic behavior previously reported. In contrast, the alkaline earth chloride solutions exhibit a reversed lyotropic trend with increasing crystallographic radius where increasing negative charge is promoted in the order BaCl 2 < SrCl 2 < CaCl 2 < MgCl 2. The origin of the opposing affinity trends is probed by testing the hypothesis that this reversal is rooted in the differing solvent structuring characteristics of the IA and IIA cations at the silica-water interface. This idea arises from earlier postulations that solvent structuring effects increase entropy through solvent disordering and these gains must be much greater than the small, positive enthalpy associated with electrostatic interactions. By correlating measured charge density with a proxy for the solvent-structuring ability of cations, this study shows that silica surface charge density is maximized by those electrolytes that have the strongest effects on solvent structuring. We suggest that for a given solid material, solvation entropy has a role in determining the ionic specificity of electrostatic interactions and reiterate the idea that the concept of lyotropy is rooted in the solvent-structuring ability of cations at the interface.

  12. The use of some ion-exchange sorbing tracer cations in in-situ experiments in high saline groundwaters

    SciTech Connect

    Byegaard, J.; Skarnemark, G.; Skaalberg, M.

    1995-12-31

    The possibility to use alkali metals and alkaline earth metals as slightly sorbing tracers in in-situ sorption experiments in high saline groundwaters has been investigated. The cation exchange characteristics of granite and some fracture minerals (chlorite and calcite) have been studied using the proposed cations as tracers. The results show low Kd`s for Na, Ca and Sr ({approximately}0.1 ml/g), while the sorption is higher for the more electropositive cations (Rb, Cs and Ba). A higher contribution of irreversible sorption can also be observed for the latter group of cations. For calcite the sorption of all the tracers, except Ca, is lower compared to the corresponding sorption to granite and chlorite. Differences in selectivity coefficients and cation exchange capacity are obtained when using different size fractions of crushed granite. The difference is even more pronounced when comparing crushed granite to intact granite.

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

    PubMed

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

    2015-02-01

    Construction of multibarrier concrete based waste disposal sites and management of alkaline mine drainage water requires cation exchangers combining excellent sorption properties with a high stability and predictable performance in hyper alkaline media. Though highly selective organic cation exchange resins have been developed for most pollutants, they can serve as a growth medium for bacterial proliferation, impairing their long-term stability and introducing unpredictable parameters into the evolution of the system. Zeolites represent a family of inorganic cation exchangers, which naturally occur in hyper alkaline conditions and cannot serve as an electron donor or carbon source for microbial proliferation. Despite their successful application as industrial cation exchangers under near neutral conditions, their performance in hyper alkaline, saline water remains highly undocumented. Using Cs(+) as a benchmark element, this study aims to assess the long-term cation exchange performance of zeolites in concrete derived aqueous solutions. Comparison of their exchange properties in alkaline media with data obtained in near neutral solutions demonstrated that the cation exchange selectivity remains unaffected by the increased hydroxyl concentration; the cation exchange capacity did however show an unexpected increase in hyper alkaline media. PMID:25569300

  14. Alkali-silica reaction resistant concrete using pumice blended cement

    NASA Astrophysics Data System (ADS)

    Ramasamy, Uma

    Durability of structures is a major challenge for the building industry. One of the many types of concrete deterioration that can affect durability is alkali-silica reaction (ASR). ASR has been found in most types of concrete structures, including dams, bridges, pavements, and other structures that are 20 to 50 years old. The degradation mechanism of ASR produces a gel that significantly expands in the presence of water as supplied from the surrounding environment. This expansion gel product can create high stresses and cracking of the concrete, which can lead to other forms of degradation and expensive structural replacement costs. The four essential factors that produce an expansive ASR gel in concrete are the presence of alkalis, siliceous aggregate, moisture, and free calcium hydroxide (CH). If concrete is starved of any one of these essential components, the expansion can be prevented. Reducing CH through the use of a supplementary cementitious material (SCM) such as natural pozzolan pumice is the focus of this research. By using a pozzolan, the amount of CH is reduced with time based on the effectiveness of the pozzolan. Many pozzolans exist, but one such naturally occurring pozzolanic material is pumice. This research focuses on determining the effect of a finely ground pumice as a SCM in terms of its resistance to ASR expansion, as well as improving resistance to other potential concrete durability mechanisms. In spite of having high alkali contents in the pumice, mixtures containing the SCM pumice more effectively mitigated the ASR expansion reaction than other degradation mechanisms. Depending on the reactivity of the aggregates and fineness of the pumice, 10-15% replacement of cement with the pumice was found to reduce the ASR expansion to the acceptable limits. The amount of CH remaining in the concrete was compared to the ASR expansion in order to improve understanding of the role of CH in the ASR reaction. Thermo-gravimetric analysis (TGA) and X

  15. 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

  16. Faraday rotation density measurements of optically thick alkali metal vapors

    NASA Astrophysics Data System (ADS)

    Vliegen, E.; Kadlecek, S.; Anderson, L. W.; Walker, T. G.; Erickson, C. J.; Happer, William

    2001-03-01

    We investigate the measurement of alkali number densities using the Faraday rotation of linearly polarized light. We find that the alkali number density may be reliably extracted even in regimes of very high buffer gas pressure, and very high alkali number density. We have directly verified our results in potassium using absorption spectroscopy on the second resonance (4 2S→5 2P).

  17. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  18. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  19. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  20. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  1. 40 CFR 721.4660 - Alcohol, alkali metal salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alcohol, alkali metal salt. 721.4660... Substances § 721.4660 Alcohol, alkali metal salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as alcohol, alkali metal salt (PMN P-91-151)...

  2. 40 CFR 721.4660 - Alcohol, alkali metal salt.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alcohol, alkali metal salt. 721.4660... Substances § 721.4660 Alcohol, alkali metal salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as alcohol, alkali metal salt (PMN P-91-151)...

  3. 40 CFR 721.4660 - Alcohol, alkali metal salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alcohol, alkali metal salt. 721.4660... Substances § 721.4660 Alcohol, alkali metal salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as alcohol, alkali metal salt (PMN P-91-151)...

  4. 40 CFR 721.4660 - Alcohol, alkali metal salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alcohol, alkali metal salt. 721.4660... Substances § 721.4660 Alcohol, alkali metal salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as alcohol, alkali metal salt (PMN P-91-151)...

  5. 40 CFR 721.4660 - Alcohol, alkali metal salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alcohol, alkali metal salt. 721.4660... Substances § 721.4660 Alcohol, alkali metal salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as alcohol, alkali metal salt (PMN P-91-151)...

  6. 40 CFR 721.5278 - Substituted naphthalenesulfonic acid, alkali salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., alkali salt. 721.5278 Section 721.5278 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5278 Substituted naphthalenesulfonic acid, alkali salt. (a) Chemical... as a substituted naphthalenesulfonic acid, alkali salt (PMN P-95-85) is subject to reporting...

  7. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., alkali salt. 721.8900 Section 721.8900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.8900 Substituted halogenated pyridinol, alkali salt. (a) Chemical... as substituted halogenated pyridinols, alkali salts (PMNs P-88-1271 and P-88-1272) are subject...

  8. 40 CFR 721.5278 - Substituted naphthalenesulfonic acid, alkali salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., alkali salt. 721.5278 Section 721.5278 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5278 Substituted naphthalenesulfonic acid, alkali salt. (a) Chemical... as a substituted naphthalenesulfonic acid, alkali salt (PMN P-95-85) is subject to reporting...

  9. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., alkali salt. 721.8900 Section 721.8900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.8900 Substituted halogenated pyridinol, alkali salt. (a) Chemical... as substituted halogenated pyridinols, alkali salts (PMNs P-88-1271 and P-88-1272) are subject...

  10. 40 CFR 721.5278 - Substituted naphthalenesulfonic acid, alkali salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., alkali salt. 721.5278 Section 721.5278 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5278 Substituted naphthalenesulfonic acid, alkali salt. (a) Chemical... as a substituted naphthalenesulfonic acid, alkali salt (PMN P-95-85) is subject to reporting...

  11. 40 CFR 721.5278 - Substituted naphthalenesulfonic acid, alkali salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., alkali salt. 721.5278 Section 721.5278 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5278 Substituted naphthalenesulfonic acid, alkali salt. (a) Chemical... as a substituted naphthalenesulfonic acid, alkali salt (PMN P-95-85) is subject to reporting...

  12. 40 CFR 721.5278 - Substituted naphthalenesulfonic acid, alkali salt.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., alkali salt. 721.5278 Section 721.5278 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5278 Substituted naphthalenesulfonic acid, alkali salt. (a) Chemical... as a substituted naphthalenesulfonic acid, alkali salt (PMN P-95-85) is subject to reporting...

  13. Symplectites in garnet megacrysts captured by alkali mafic magma

    NASA Astrophysics Data System (ADS)

    Aseeva, Anna; Vysotskiy, Sergey; Karabtsov, Alexander; Alexandrov, Igor; Chashchin, Alexander

    2014-05-01

    Megacrysts are widespread in Cenozoic alkali-basalts of many volcanic provinces of the world. Garnet megacrysts containing symplectites are the most interesting, as can be used for reconstruction of physical and chemical conditions in liquid basalt at the moment of garnet crystal capture. The collection of garnet megacrysts and garnet-pyroxene aggregates from Shavaryn-Tsaram (Hangaj plateau, Mongolia) and Bartoj (Dzhida basaltic field, Russia) paleovolcanoes has studied. Cenozoic alkali basaltic volcanism of these two spatially separated areas is considered to be related to a uniform process of lithosphere spreading in Baikal and related Central Asian rift systems. The studying of garnet-pyroxene aggregate and fragments of garnet megacrysts from these two paleovolcanoes revealed two mineral associations: primary and secondary. The former includes garnet and clinopyroxene, the letter (symplectite) is presented by products of garnet disintegration (clinopyroxene remain unaltered). At least two paragenesis can be allocated: 1) shpinel - plagioclase-olivine sometimes with gedrite and orthopyroxene; 2) olivine (with glass). Experimental modeling of decomposition process in garnet megacryst has been carried out with the help of 'Selector' softwear at various P-T parameters. Physical and chemical conditions of this paragenesis occurrence have also been estimated by up-to-date geothermometers and geobarometers (T 950-1000 C, P 4-4.5 kbar. Conclusions: 1. Garnet megacrysts are apparently in non-equilibrium with alkali-basalts. They were formed in conditions corresponding to zones of mantle plums at the bottom of crust, in magmatic chambers at constant infiltration of fluid. Subsequently megacrysts were captured by alkali-basalt magma and taken out to the surface. 2. Kelyphitic rims on garnet megacrysts is a result of partial melting of megacrysts on interaction with the hosting alkali basaltic rock. During melting garnet transforms with the formation of Na-K glass and Mg

  14. Preparing cationic cotton linter cellulose with high substitution degree by ultrasonic treatment.

    PubMed

    Zhang, Fulong; Pang, Zhiqiang; Dong, Cuihua; Liu, Zong

    2015-11-01

    As an important cellulose derivative, cationic cellulose has becoming an attractive material. However, it remains challenging to produce cationic cellulose with high substitute degree. In this paper, we successfully increased the substitute degree of cationic cellulose by introducing ultrasonic treatment, which efficiently breaks hydrogen bonds of the chemical structure of cationic cellulose. Properties of cationic cellulose were studied by scanning electron spectroscope (SEM), contact angle, X-ray diffraction (XRD) and thermogravimetric analysis (TGA). Experimental results show that the cationic cellulose has rougher surface and lower crystallinity degree as compared to the original sample. TGA analysis verifies that the thermostability of CLC decreases after the cationic modification. The residual of the cationic cellulose (25 wt%) after pyrolysis increases significantly as compared to that of the original cellulose (15 wt%). PMID:26256343

  15. Computational studies of solid-state alkali conduction in rechargeable alkali-ion batteries

    DOE PAGESBeta

    Deng, Zhi; Mo, Yifei; Ong, Shyue Ping

    2016-03-25

    The facile conduction of alkali ions in a crystal host is of crucial importance in rechargeable alkali-ion batteries, the dominant form of energy storage today. In this review, we provide a comprehensive survey of computational approaches to study solid-state alkali diffusion. We demonstrate how these methods have provided useful insights into the design of materials that form the main components of a rechargeable alkali-ion battery, namely the electrodes, superionic conductor solid electrolytes and interfaces. We will also provide a perspective on future challenges and directions. Here, the scope of this review includes the monovalent lithium- and sodium-ion chemistries that aremore » currently of the most commercial interest.« less

  16. Alkali resistant optical coatings for alkali lasers and methods of production thereof

    DOEpatents

    Soules, Thomas F; Beach, Raymond J; Mitchell, Scott C

    2014-11-18

    In one embodiment, a multilayer dielectric coating for use in an alkali laser includes two or more alternating layers of high and low refractive index materials, wherein an innermost layer includes a thicker, >500 nm, and dense, >97% of theoretical, layer of at least one of: alumina, zirconia, and hafnia for protecting subsequent layers of the two or more alternating layers of high and low index dielectric materials from alkali attack. In another embodiment, a method for forming an alkali resistant coating includes forming a first oxide material above a substrate and forming a second oxide material above the first oxide material to form a multilayer dielectric coating, wherein the second oxide material is on a side of the multilayer dielectric coating for contacting an alkali.

  17. Terahertz radiation in alkali vapor plasmas

    SciTech Connect

    Sun, Xuan; Zhang, X.-C.

    2014-05-12

    By taking advantage of low ionization potentials of alkali atoms, we demonstrate terahertz wave generation from cesium and rubidium vapor plasmas with an amplitude nearly one order of magnitude larger than that from nitrogen gas at low pressure (0.02–0.5 Torr). The observed phenomena are explained by the numerical modeling based upon electron tunneling ionization.

  18. The Additive Coloration of Alkali Halides

    ERIC Educational Resources Information Center

    Jirgal, G. H.; and others

    1969-01-01

    Describes the construction and use of an inexpensive, vacuum furnace designed to produce F-centers in alkali halide crystals by additive coloration. The method described avoids corrosion or contamination during the coloration process. Examination of the resultant crystals is discussed and several experiments using additively colored crystals are…

  19. Involvement of NADPH oxidases in alkali burn-induced corneal injury

    PubMed Central

    GU, XUE-JUN; LIU, XIAN; CHEN, YING-YING; ZHAO, YAO; XU, MAN; HAN, XIAO-JIAN; LIU, QIU-PING; YI, JING-LIN; LI, JING-MING

    2016-01-01

    Chemical burns are a major cause of corneal injury. Oxidative stress, inflammatory responses and neovascularization after the chemical burn aggravate corneal damage, and lead to loss of vision. Although NADPH oxidases (Noxs) play a crucial role in the production of reactive oxygen species (ROS), the role of Noxs in chemical burn-induced corneal injury remains to be elucidated. In the present study, the transcription and expression of Noxs in corneas were examined by RT-qPCR, western blot analysis and immunofluorescence staining. It was found that alkali burns markedly upregulated the transcription and expression of Nox2 and Nox4 in human or mouse corneas. The inhibition of Noxs by diphenyleneiodonium (DPI) or apocynin (Apo) effectively attenuated alkali burn-induced ROS production and decreased 3-nitrotyrosine (3-NT) protein levels in the corneas. In addition, Noxs/CD11b double-immunofluorescence staining indicated that Nox2 and Nox4 were partially co-localized with CD11b. DPI or Apo prevented the infiltration of CD11b-positive inflammatory cells, and inhibited the transcription of inflammatory cytokines following alkali burn-induced corneal injury. In our mouse model of alkali burn-induced corneal injury, corneal neovascularization (CNV) occurred on day 3, and it affected 50% of the whole area of the cornea on day 7, and on day 14, CNV coverage of the cornea reached maximum levels. DPI or Apo effectively attenuated alkali burn-induced CNV and decreased the mRNA levels of angiogenic factors, including vascular endothelial growth factor (VEGF), VEGF receptors and matrix metalloproteinases (MMPs). Taken together, our data indicate that Noxs play a role in alkali burn-induced corneal injury by regulating oxidative stress, inflammatory responses and CNV, and we thus suggest that Noxs are a potential therapeutic target in the future treatment of chemical-induced corneal injury. PMID:27221536

  20. Synergistic capture mechanisms for alkali and sulfur species from combustion. Final report

    SciTech Connect

    Peterson, T.W.; Shadman, F.; Wendt, J.O.L.; Mwabe, P.O.

    1994-02-01

    Experimental work was carried out on a 17 kW, 600 cm long, gas laboratory combustor, to investigate the post flame reactive capture of alkali species by kaolinite. Emphasis was on alkali/sorbent interactions occurring in flue gas at temperatures above the alkali dewpoint and on the formation of water insoluble reaction products. Time-temperature studies were carried out by injecting kaolinite at different axial points along the combustor. The effect of chlorine and sulfur on alkali capture was investigated by doping the flame with SO{sub 2} and Cl{sub 2} gases to simulate coal flame environments. Particle time and temperature history was kept as close as possible to that which would ordinarily be found in a practical boiler. Experiments designed to extract apparent initial reaction rates were carried using a narrow range, 1-2 {mu}m modal size sorbent, while, a coarse, multi size sorbent was used to investigate the governing transport mechanisms. The capture reaction has been proposed to be between alkali hydroxide and activated kaolinite, and remains so in the presence of sulfur and chlorine. The presence of sulfur reduces sodium capture by under 10% at 1300{degree}C. Larger reductions at lower temperatures are attributed to the elevated dewpoint of sodium ({approximately}850{degree}C) with subsequent reduction in sorbent residence time in the alkali gas phase domain. Chlorine reduces sodium capture by 30% across the temperature range covered by the present experiments. This result has been linked to thermodynamic equilibria between sodium hydroxide, sodium chloride and water.

  1. Self-assembly of Alkali-uranyl-peroxide Clusters

    SciTech Connect

    Nyman, May; Rodriquez, Mark A.; Campana, Charles F.

    2010-08-11

    The hexavalent uranium specie, uranyl triperoxide, UO2(O2)34-, has been shown recently to behave like high oxidation-state d0 transition-metals, self-assembling into polyoxometalate-like clusters that contain up to 60 uranyl cations bridged by peroxide ligands. There has been much less focus on synthesis and structural characterization of salts of the monomeric UO2(O2)34- building block of these clusters. However, these could serve as water-soluble uranyl precursors for both clusters and materials, and also be used as simple models to study aqueous behavior by experiment and modeling. The countercation is of utmost importance to the assembly of these clusters, and Li+ has proven useful for the crystallization of many of the known cluster geometries to date. We present in this paper synthesis and structural characterization of two monomeric lithium uranyl-peroxide salts, Li4[UO2(O2)3]·10H2O (1) and [UO2(O2)3]12[(UO2(OH)4)Li16(H2O)28]3·Li6[H2O]26 (2). They were obtained from aqueous-alcohol solutions rather than the analogous aqueous solutions from which lithium uranyl-peroxide clusters are crystallized. Rapid introduction of the alcohol gives the structure of (1) whereas slow diffusion of alcohol results in crystallization of (2). (2) is an unusual structure featuring uranyl-centered alkali clusters that are linked into ring and spherical arrangements via [UO2(O2)3] anions. Furthermore, partial substitution of Rb or Cs into the synthesis results in formation of (2) with substitution of these larger alkalis into the uranyl-centered clusters. We surmise that the slow crystallization allows for direct bonding of alkali metals to the

  2. Gel nanostructure in alkali-activated binders based on slag and fly ash, and effects of accelerated carbonation

    SciTech Connect

    Bernal, Susan A.; Provis, John L.; Walkley, Brant; San Nicolas, Rackel; Gehman, John D.; Brice, David G.; Kilcullen, Adam R.; Duxson, Peter; Deventer, Jannie S.J. van

    2013-11-15

    Binders formed through alkali-activation of slags and fly ashes, including ‘fly ash geopolymers’, provide appealing properties as binders for low-emissions concrete production. However, the changes in pH and pore solution chemistry induced during accelerated carbonation testing provide unrealistically low predictions of in-service carbonation resistance. The aluminosilicate gel remaining in an alkali-activated slag system after accelerated carbonation is highly polymerised, consistent with a decalcification mechanism, while fly ash-based binders mainly carbonate through precipitation of alkali salts (bicarbonates at elevated CO{sub 2} concentrations, or carbonates under natural exposure) from the pore solution, with little change in the binder gel identifiable by nuclear magnetic resonance spectroscopy. In activated fly ash/slag blends, two distinct gels (C–A–S–H and N–A–S–H) are formed; under accelerated carbonation, the N–A–S–H gel behaves comparably to fly ash-based systems, while the C–A–S–H gel is decalcified similarly to alkali-activated slag. This provides new scope for durability optimisation, and for developing appropriate testing methodologies. -- Highlights: •C-A-S-H gel in alkali-activated slag decalcifies during accelerated carbonation. •Alkali-activated fly ash gel changes much less under CO{sub 2} exposure. •Blended slag-fly ash binder contains two coexisting gel types. •These two gels respond differently to carbonation. •Understanding of carbonation mechanisms is essential in developing test methods.

  3. The relation between net calcium, alkali cation and chloride movements in red cells exposed to salicylate.

    PubMed Central

    Bürgin, H; Schatzmann, H J

    1979-01-01

    1. From a 150 mM-NH4 salicylate medium salicylate enters human red cells with a rate constant of 1.9 min-1 at 0 degrees C. 2. Salicylate increases the red cell permeability for Ca2+ (and Mg2+). There is no saturation of the Ca2+ transfer with respect to salicylate up to 150 mM and with respect to external Ca2+ up to 30 mM. 3. Ca2+ entering from salicylate media activates the Ca-sensitive K channel present in human but not in adult ruminant red cells. 4. The increase in K permeability which ensues hyperpolarizes the membrane in Na salicylate media, accelerating further Ca2+ entry and Mg2+ entry and favouring Cl- loss (see Fig. 8). The Ca2+ inward movement is in agreement with the constant field equation if the membrane potential is assumed to equal the K equilibrium potential and if two charges are attributed to the mobile species. 5. The effect of salicylate on Ca2+ permeability and hence its sequelae are reversible upon washing the cells. 6. 3-OH-benzoic acid and 4-OH-benzoic acid do not exert the effect salicylate has on Ca2+ permeability. 7. In 150 mM-Na salicylate media the Cl--salicylate exchange is virtually nil at 0 degrees C. The exchange seen at 19 degrees C is obviously not across the anion exchange mechanism and proceeds at a rate comparable to that for Cl- movement in the nonexchange-restricted mode given by Hunter (1971, 1977) for cells in a normal medium. 8. Ca2+ seems to increase the Cl- permeability seen under these conditions. 9. The possibility that salicylate acts as an ionophore for Ca2+ is discussed. PMID:430388

  4. Optical probes for the detection of protons, and alkali and alkaline earth metal cations.

    PubMed

    Hamilton, Graham R C; Sahoo, Suban K; Kamila, Sukanta; Singh, Narinder; Kaur, Navneet; Hyland, Barry W; Callan, John F

    2015-07-01

    Luminescent sensors and switches continue to play a key role in shaping our understanding of key biochemical processes, assist in the diagnosis of disease and contribute to the design of new drugs and therapies. Similarly, their contribution to the environment cannot be understated as they offer a portable means to undertake field testing for hazardous chemicals and pollutants such as heavy metals. From a physiological perspective, the Group I and II metal ions are among the most important in the periodic table with blood plasma levels of H(+), Na(+) and Ca(2+) being indicators of several possible disease states. In this review, we examine the progress that has been made in the development of luminescent probes for Group I and Group II ions as well as protons. The potential applications of these probes and the mechanism involved in controlling their luminescent response upon analyte binding will also be discussed. PMID:25742963

  5. Bisphenols that stimulate cells to release alkali metal cations: a structure-activity study.

    PubMed

    Hopp, L; Megee, S O; Lloyd, J B

    1998-10-22

    The laxative action of phenolphthalein (5) is believed to result from induction of potassium and water efflux from the colon epithelium. In cultured cells, K+ efflux is promoted by 5 and by a contaminant (1) present in commercial phenol red. Six compounds with chemical structures related to those of 5 and 1 were tested for ability to induce the release of 86Rb from COS-7 cells preloaded with this isotope: 4,4'-(9-fluorenylidene)diphenol (2), 4, 4'-(9-fluorenylidene)dianiline, 4, 4'-(9-fluorenylidene)bisphenoxyethanol, 1,1'-bi-2-naphthol, 4, 4'-biphenol, and bis(4-hydroxyphenyl)methane. With one exception these compounds were all inactive at a concentration of 10 microM. However, 2 caused profound 86Rb efflux at concentrations as low as 100 nM. Concentrations of 5 1-2 orders of magnitude higher were needed to achieve similar levels of activity. The three compounds known to be active in this experimental system share a common feature that is absent in all the inactive compounds: a five-membered ring structure, one of whose carbon atoms is disubstituted with p-hydroxyphenyl residues. Because 2 and 5 are readily available, comparative studies on the mechanism of action of these biphenols at the cellular level can now be undertaken. PMID:9784117

  6. POTENTIAL-MODULATED INTERCALATION OF ALKALI CATIONS INTO METAL HEXACYANOFERRATE COATED ELECTRODES

    EPA Science Inventory

    The current baseline technology for separating radiocesium (137Cs) from liquid wastes is traditional ion exchange, where chemical regeneration of the ion exchange bed can generate many bed volumes of secondary rinse and regeneration waste solution during each exchange cycle. Chem...

  7. Novel Pendant Benzene Disulfonic Acid Blended SPPO Membranes for Alkali Recovery: Fabrication and Properties.

    PubMed

    Mondal, Abhishek N; Dai, Chunhua; Pan, Jiefeng; Zheng, Chunlei; Hossain, Md Masem; Khan, Muhammad Imran; Wu, Liang; Xu, Tongwen

    2015-07-29

    To reconcile the trade-off between separation performance and availability of desired material for cation exchange membranes (CEMs), we designed and successfully prepared a novel sulfonated aromatic backbone-based cation exchange precursor named sodium 4,4'-(((((3,3'-disulfo-[1,1'-biphenyl]-4,4'-diyl)bis(oxy)) bis(4,1-phenylene))bis(azanediyl))bis(methylene))bis(benzene-1,3-disulfonate) [DSBPB] from 4,4'-bis(4-aminophenoxy)-[1,1'-biphenyl]-3,3'-disulfonic acid [BAPBDS] by a three-step procedure that included sulfonation, Michael condensation followed by reduction. Prepared DSBPB was used to blend with sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (SPPO) to get CEMs for alkali recovery via diffusion dialysis. Physiochemical properties and electrochemical performance of prepared membranes can be tuned by varying the dosage of DSBPB. All the thermo-mechanical properties like DMA and TGA were investigated along with water uptake (WR), ion exchange capacity (IEC), dimensional stability, etc. The effect of DSBPB was discussed in brief in connection with alkali recovery and ion conducting channels. The SPPO/DSBPB membranes possess both high water uptake as well as ion exchange capacity with high thermo-mechanical stability. At 25 °C the dialysis coefficients (UOH) appeared to be in the range of 0.0048-0.00814 m/h, whereas the separation factor (S) ranged from 12.61 to 36.88 when the membranes were tested for base recovery in Na2WO4/NaOH waste solution. Prepared membranes showed much improved DD performances compared to traditional SPPO membrane and possess the potentiality to be a promising candidate for alkali recovery via diffusion dialysis. PMID:26146932

  8. Physics and chemistry of alkali-silica reactions

    SciTech Connect

    Diamond, S.; Barneyback, R.S. Jr.; Struble, L.J.

    1981-01-01

    The philosophy underlying recent research on alkali-silica reactions is reviewed and illustrations of recent results are provided. It has been possible to follow the kinetics of the chemical reaction between dissolved alkalis and opal in mortars by monitoring the rate at which alkalis are removed from the pore solutions of reacting mortars. Studies of the expansion behavior of synthetic alkali silica gels under controlled conditions were carried out and show no obvious correlation to chemical composition. The alkali reaction in mortars was found to produce changes in the appearance of opal grains documentable by the use of a scanning electron microscope.

  9. Calcium-Alkali Syndrome in the Modern Era

    PubMed Central

    Patel, Ami M.; Adeseun, Gbemisola A.; Goldfarb, Stanley

    2013-01-01

    The ingestion of calcium, along with alkali, results in a well-described triad of hypercalcemia, metabolic alkalosis, and renal insufficiency. Over time, the epidemiology and root cause of the syndrome have shifted, such that the disorder, originally called the milk-alkali syndrome, is now better described as the calcium-alkali syndrome. The calcium-alkali syndrome is an important cause of morbidity that may be on the rise, an unintended consequence of shifts in calcium and vitamin D intake in segments of the population. We review the pathophysiology of the calcium-alkali syndrome. PMID:24288027

  10. Alkali metal recovery from carbonaceous material conversion process

    DOEpatents

    Sharp, David W.; Clavenna, LeRoy R.; Gorbaty, Martin L.; Tsou, Joe M.

    1980-01-01

    In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced in the gasifier or similar reaction zone, alkali metal constitutents are recovered from the particles by withdrawing and passing the particles from the reaction zone to an alkali metal recovery zone in the substantial absence of molecular oxygen and treating the particles in the recovery zone with water or an aqueous solution in the substantial absence of molecular oxygen. The solution formed by treating the particles in the recovery zone will contain water-soluble alkali metal constituents and is recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst. Preventing contact of the particles with oxygen as they are withdrawn from the reaction zone and during treatment in the recovery zone avoids the formation of undesirable alkali metal constituents in the aqueous solution produced in the recovery zone and insures maximum recovery of water-soluble alkali metal constituents from the alkali metal residues.

  11. Alkali element background reduction in laser ICP-MS

    NASA Astrophysics Data System (ADS)

    Magee, C. W., Jr.; Norris, C. A.

    2014-11-01

    Alkali backgrounds in laser ablation ICP-MS analyses can be enhanced by electron-induced ionization of alkali contamination on the skimmer cone, reducing effective detection limits for these elements. Traditionally, this problem is addressed by isolating analyses of high alkali materials onto a designated cone set, or by operating the ICP-MS in a "soft extraction" mode, which reduces the energy of electrons repelled into the potentially contaminated sampling cone by the extraction field. Here we present a novel approach, where we replace the traditional alkali glass tuning standards with synthetic low-alkali glass reference materials. Using this vitreous tuning solution, we find that this approach reduces the amount of alkali contamination produced, halving backgrounds for the heavy alkali elements without any change to analytical procedures. Using segregated cones is still the most effective method for reducing lithium backgrounds, but since the procedures are complimentary both can easily be applied to the routine operations of an analytical lab.

  12. Alkali element background reduction in laser ICP-MS

    NASA Astrophysics Data System (ADS)

    Magee, C. W., Jr.; Norris, C. A.

    2015-03-01

    Alkali backgrounds in laser ablation ICP-MS analyses can be enhanced by electron-induced ionisation of alkali contamination on the skimmer cone, reducing effective detection limits for these elements. Traditionally, this problem is addressed by isolating analyses of high-alkali materials onto a designated cone set, or by operating the ICP-MS in a "soft extraction" mode, which reduces the energy of electrons repelled into the potentially contaminated sampling cone by the extraction field. Here we present a novel approach, where we replace the traditional alkali glass tuning standards with synthetic low-alkali glass reference materials. Using this vitreous tuning solution, we find that this approach reduces the amount of alkali contamination produced, halving backgrounds for the heavy alkali elements without any change to analytical procedures. Using segregated cones is still the most effective method for reducing lithium backgrounds, but since the procedures are complimentary, both can easily be applied to the routine operations of an analytical lab.

  13. Heterovalent substitutions in garnet and their implications for diffusion of Y+REEs and alkalis (Invited)

    NASA Astrophysics Data System (ADS)

    Carlson, W. D.; Gale, J. D.; Wright, K.

    2013-12-01

    Lattice-dynamics calculations in the static limit suggest that large trivalent ions (Y+REEs) are incorporated into garnet primarily by means of substitutions that introduce menzerite and alkali components. The diffusion mechanisms implied by this finding explain otherwise puzzling aspects of recent determinations of diffusion rates for Y+REEs and Li in natural systems, bolstering confidence in the validity of those rates. Several substitution schemes have been proposed to provide the charge-balance required for incorporation of trivalent Y+REEs substituting for divalent cations in dodecahedral sites in aluminosilicate garnet: (1) YAG components, with tetrahedral Al; (2) vacancy components, with one unoccupied dodecahedral site for each two trivalent ions; (3) alkali components, with dodecahedral Na or Li; (4) menzerite components, with octahedral Mg or Fe; and (5) Y2Li components, with octahedral Li compensating for a pair of Y+REE ions. The relative energetic costs of these substitutions were evaluated in pyrope, almandine, spessartine and grossular by means of lattice-dynamics calculations at T = 0 K and P = 0 GPa, using well-established force-field potentials, and referencing exchange energies to the lattice energies of binary oxides as sources/sinks for the exchanged ions. Energies calculated for the incorporation of menzerite and alkali components are appreciably lower than those for the YAG component, and very substantially lower than those for the other components. Provided that the relative energetic costs are similar at elevated T and P to those in the static limit (testing of this assumption is currently underway), the menzerite and alkali substitutions should predominate in natural aluminosilicate garnets, the YAG substitution should play only a subordinate role, and the other substitutions should be near-negligible. As a result, diffusion mechanisms for Y+REEs in garnet require that motion of these elements must be coupled to transport of either

  14. Influence of lithium hydroxide on alkali-silica reaction

    SciTech Connect

    Bulteel, D.; Garcia-Diaz, E.; Degrugilliers, P.

    2010-04-15

    Several papers show that the use of lithium limits the development of alkali-silica reaction (ASR) in concrete. The aim of this study is to improve the understanding of lithium's role on the alteration mechanism of ASR. The approach used is a chemical method which allowed a quantitative measurement of the specific degree of reaction of ASR. The chemical concrete sub-system used, called model reactor, is composed of the main ASR reagents: reactive aggregate, portlandite and alkaline solution. Different reaction degrees are measured and compared for different alkaline solutions: NaOH, KOH and LiOH. Alteration by ASR is observed with the same reaction degrees in the presence of NaOH and KOH, accompanied by the consumption of hydroxyl concentration. On the other hand with LiOH, ASR is very limited. Reaction degree values evolve little and the hydroxyl concentration remains about stable. These observations demonstrate that lithium ions have an inhibitor role on ASR.

  15. 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

  16. Developments in alkali-metal atomic magnetometry

    NASA Astrophysics Data System (ADS)

    Seltzer, Scott Jeffrey

    Alkali-metal magnetometers use the coherent precession of polarized atomic spins to detect and measure magnetic fields. Recent advances have enabled magnetometers to become competitive with SQUIDs as the most sensitive magnetic field detectors, and they now find use in a variety of areas ranging from medicine and NMR to explosives detection and fundamental physics research. In this thesis we discuss several developments in alkali-metal atomic magnetometry for both practical and fundamental applications. We present a new method of polarizing the alkali atoms by modulating the optical pumping rate at both the linear and quadratic Zeeman resonance frequencies. We demonstrate experimentally that this method enhances the sensitivity of a potassium magnetometer operating in the Earth's field by a factor of 4, and we calculate that it can reduce the orientation-dependent heading error to less than 0.1 nT. We discuss a radio-frequency magnetometer for detection of oscillating magnetic fields with sensitivity better than 0.2 fT/ Hz , which we apply to the observation of nuclear magnetic resonance (NMR) signals from polarized water, as well as nuclear quadrupole resonance (NQR) signals from ammonium nitrate. We demonstrate that a spin-exchange relaxation-free (SERF) magnetometer can measure all three vector components of the magnetic field in an unshielded environment with comparable sensitivity to other devices. We find that octadecyltrichlorosilane (OTS) acts as an anti-relaxation coating for alkali atoms at temperatures below 170°C, allowing them to collide with a glass surface up to 2,000 times before depolarizing, and we present the first demonstration of high-temperature magnetometry with a coated cell. We also describe a reusable alkali vapor cell intended for the study of interactions between alkali atoms and surface coatings. Finally, we explore the use of a cesium-xenon SERF comagnetometer for a proposed measurement of the permanent electric dipole moments (EDMs

  17. The effects of acid and alkali modification on the adsorption performance of fuller's earth for basic dye.

    PubMed

    Hisarli, G

    2005-01-01

    The objective of this work was to prepare modified adsorbents from fuller's earth (FE) by acid and alkali treatment for enhancement cationic dye adsorption. Toluidine blue (TB) was selected as adsorbate for evaluating the adsorption performance of fuller's earth samples, which was affected significantly by acid and alkali modification. The adsorption of TB was studied by visible spectra. The absorption band of the monomer at low loading of TB in FE suspension with respect to its maximum in aqueous solution is red-shifted, which is related to accessibility of dye interlamellar space in the presence of positively charged surface sites. Since all surfaces are negatively charged under experimental conditions, this effect has not been observed in acid- and alkali-treated FE suspensions. It was seen that the adsorption capacity of alkali-treated surface (FEAl) for TB was higher than these of acid-treated adsorbent (FEAc) and FE. Scanning electron micrographs (SEM) and X-ray diffraction (XRD) and fluorescence (XRF) spectra were applied to analyze the structure of the raw and modified FE samples. Absence of any identifiable amount of a crystalline compound in the solid reaction products after acid treatment was confirmed by XRD and SEM, whereas the crystalline form of FEAl was preserved. Experimental data for high-concentration regions were well described by Freundlich and Langmuir adsorption equations. The thermodynamic parameters were estimated for FE, FEAc, and FEAl by using temperature dependence of adsorption equilibrium constants. PMID:15567375

  18. Effect of alkali lignins with different molecular weights from alkali pretreated rice straw hydrolyzate on enzymatic hydrolysis.

    PubMed

    Li, Yun; Qi, Benkun; Luo, Jianquan; Wan, Yinhua

    2016-01-01

    This study investigated the effect of alkali lignins with different molecular weights on enzymatic hydrolysis of lignocellulose. Different alkali lignins fractions, which were obtained from cascade ultrafiltration, were added into the dilute acid pretreated (DAP) and alkali pretreated (AP) rice straws respectively during enzymatic hydrolysis. The results showed that the addition of alkali lignins enhanced the hydrolysis and the enhancement for hydrolysis increased with increasing molecular weights of alkali lignins, with maximum enhancement being 28.69% for DAP and 20.05% for AP, respectively. The enhancement was partly attributed to the improved cellulase activity, and filter paper activity increased by 18.03% when adding lignin with highest molecular weight. It was found that the enhancement of enzymatic hydrolysis was correlated with the adsorption affinity of cellulase on alkali lignins, and the difference in surface charge and hydrophobicity of alkali lignins were responsible for the difference in affinity between cellulase and lignins. PMID:26496216

  19. Removal of Retired Alkali Metal Test Systems

    SciTech Connect

    BREHM, W.F.

    2003-01-01

    This paper describes the successful effort to remove alkali metals, alkali metal residues, and piping and structures from retired non-radioactive test systems on the Hanford Site. These test systems were used between 1965 and 1982 to support the Fast Flux Test Facility and the Liquid Metal Fast Breeder Reactor Program. A considerable volume of sodium and sodium-potassium alloy (NaK) was successfully recycled to the commercial sector; structural material and electrical material such as wiring was also recycled. Innovative techniques were used to safely remove NaK and its residues from a test system that could not be gravity-drained. The work was done safely, with no environmental issues or significant schedule delays.

  20. Removal of Retired Alkali Metal Test Systems

    SciTech Connect

    Brehm, W. F.; Church, W. R.; Biglin, J. W.

    2003-02-26

    This paper describes the successful effort to remove alkali metals, alkali metal residues, and piping and structures from retired non-radioactive test systems on the Hanford Site. These test systems were used between 1965 and 1982 to support the Fast Flux Test Facility and the Liquid Metal Fast Breeder Reactor Program. A considerable volume of sodium and sodium-potassium alloy (NaK) was successfully recycled to the commercial sector; structural material and electrical material such as wiring was also recycled. Innovative techniques were used to safely remove NaK and its residues from a test system that could not be gravity-drained. The work was done safely, with no environmental issues or significant schedule delays.

  1. Geopolymers and Related Alkali-Activated Materials

    NASA Astrophysics Data System (ADS)

    Provis, John L.; Bernal, Susan A.

    2014-07-01

    The development of new, sustainable, low-CO2 construction materials is essential if the global construction industry is to reduce the environmental footprint of its activities, which is incurred particularly through the production of Portland cement. One type of non-Portland cement that is attracting particular attention is based on alkali-aluminosilicate chemistry, including the class of binders that have become known as geopolymers. These materials offer technical properties comparable to those of Portland cement, but with a much lower CO2 footprint and with the potential for performance advantages over traditional cements in certain niche applications. This review discusses the synthesis of alkali-activated binders from blast furnace slag, calcined clay (metakaolin), and fly ash, including analysis of the chemical reaction mechanisms and binder phase assemblages that control the early-age and hardened properties of these materials, in particular initial setting and long-term durability. Perspectives for future research developments are also explored.

  2. Quantum magnetism of alkali Rydberg atoms

    NASA Astrophysics Data System (ADS)

    Malinovskaya, Svetlana; Liu, Gengyuan

    2016-05-01

    We discuss a method to control dynamics in many-body spin states of 87Rb Rydberg atoms. The method permits excitation of cold gases and form ordered structures of alkali atoms. It makes use of a two-photon excitation scheme with circularly polarized and linearly chirped pulses. The method aims for controlled quantum state preparation in large ensembles. It is actual for experiments studding the spin hopping dynamics and realization of quantum random walks.

  3. Alkali Metal Heat Pipe Life Issues

    NASA Technical Reports Server (NTRS)

    Reid, Robert S.

    2004-01-01

    One approach to space fission power system design is predicated on the use of alkali metal heat pipes, either as radiator elements, thermal management components, or as part of the core primary heat-transfer system. This synopsis characterizes long-life core heat pipes. References are included where more detailed information can be found. Specifics shown here are for demonstrational purposes and do not necessarily reflect current Project Prometheus point designs.

  4. Alkali metal protective garment and composite material

    SciTech Connect

    Ballif, J.L.; Yuan, W.W.

    1980-09-16

    A protective garment and composite material providing satisfactory heat resistance and physical protection for articles and personnel exposed to hot molten alkali metals, such as sodium are described. Physical protection is provided by a continuous layer of nickel foil. Heat resistance is provided by an underlying backing layer of thermal insulation. Overlying outer layers of fireproof woven ceramic fibers are used to protect the foil during storage and handling.

  5. Alkali metal protective garment and composite material

    SciTech Connect

    Ballif, III, John L.; Yuan, Wei W.

    1980-01-01

    A protective garment and composite material providing satisfactory heat resistance and physical protection for articles and personnel exposed to hot molten alkali metals, such as sodium. Physical protection is provided by a continuous layer of nickel foil. Heat resistance is provided by an underlying backing layer of thermal insulation. Overlying outer layers of fireproof woven ceramic fibers are used to protect the foil during storage and handling.

  6. Study of superconducting state parameters of alkali alkali binary alloys by a pseudopotential

    NASA Astrophysics Data System (ADS)

    Vora, Aditya M.

    2006-12-01

    A detailed study of the superconducting state parameters (SSP) viz. electron-phonon coupling strength λ, Coulomb pseudopotential μ∗, transition temperature TC, isotope effect exponent α and effective interaction strength N OV of ten alkali-alkali binary alloys i.e. Li 1- xNa x, Li 1- xK x, Li 1- xRb x, Li 1- xCs x, Na 1- xK x, Na 1- xRb x, Na 1- xCs x, K 1- xRb x, K 1- xCs x and Rb 1- xCs x are made within the framework of the model potential formalism and employing the pseudo-alloy-atom (PAA) model for the first time. We use the Ashcroft’s empty core (EMC) model potential for evaluating the superconducting properties of alkali alloys. Five different forms of local field correction functions viz. Hartree (H), Taylor (T), Ichimaru-Utsumi (IU), Farid et al. (F) and Sarkar et al. (S) are used to incorporate the exchange and correlation effects. A considerable influence of various exchange and correlation functions on λ and μ∗ is found from the present study. Reasonable agreement with the theoretical values of the SSP of pure components is found (corresponding to the concentration x = 0 or 1). It is also concluded that nature of the SSP strongly depends on the value of the atomic volume Ω0 of alkali-alkali binary alloys.

  7. Transport properties of alkali metal doped fullerides

    SciTech Connect

    Yadav, Daluram Yadav, Nishchhal

    2015-07-31

    We have studied the intercage interactions between the adjacent C{sub 60} cages and expansion of lattice due to the intercalation of alkali atoms based on the spring model to estimate phonon frequencies from the dynamical matrix for the intermolecular alkali-C{sub 60} phonons. We considered a two-peak model for the phonon density of states to investigate the nature of electron pairing mechanism for superconducting state in fullerides. Coulomb repulsive parameter and the electron phonon coupling strength are obtained within the random phase approximation. Transition temperature, T{sub c}, is obtained in a situation when the free electrons in lowest molecular orbital are coupled with alkali-C{sub 60} phonons as 5 K, which is much lower as compared to reported T{sub c} (20 K). The superconducting pairing is mainly driven by the high frequency intramolecular phonons and their effects enhance it to 22 K. The importance of the present study, the pressure effect and normal state transport properties are calculated within the same model leading superconductivity.

  8. Transport properties of alkali metal doped fullerides

    NASA Astrophysics Data System (ADS)

    Yadav, Daluram; Yadav, Nishchhal

    2015-07-01

    We have studied the intercage interactions between the adjacent C60 cages and expansion of lattice due to the intercalation of alkali atoms based on the spring model to estimate phonon frequencies from the dynamical matrix for the intermolecular alkali-C60 phonons. We considered a two-peak model for the phonon density of states to investigate the nature of electron pairing mechanism for superconducting state in fullerides. Coulomb repulsive parameter and the electron phonon coupling strength are obtained within the random phase approximation. Transition temperature, Tc, is obtained in a situation when the free electrons in lowest molecular orbital are coupled with alkali-C60 phonons as 5 K, which is much lower as compared to reported Tc (20 K). The superconducting pairing is mainly driven by the high frequency intramolecular phonons and their effects enhance it to 22 K. The importance of the present study, the pressure effect and normal state transport properties are calculated within the same model leading superconductivity.

  9. Characterization of Adsorbed Alkali Metal Ions in 2:1 Type Clay Minerals from First-Principles Metadynamics.

    PubMed

    Ikeda, Takashi; Suzuki, Shinichi; Yaita, Tsuyoshi

    2015-07-30

    Adsorption states of alkali metal ions in three kinds of 2:1 type clay minerals are systematically investigated via first-principles-based metadynamics. Our reconstructed free energy surfaces in a two-dimensional space of coordination numbers specifically employed as collective variables for describing the interlayer cations show that an inner-sphere (IS) complex is preferentially formed for Cs(+) in the 2:1 type trioctahedral clay minerals with saponite-like compositions, where lighter alkali metal ions show a tendency to form an outer-sphere one instead. The strong preference for an IS complex observed for Cs(+) is found to result partially from the capability of recognizing selectively Cs(+) ions at the basal O atoms with the Lewis basicity significantly enhanced by the isomorphic substitution in tetrahedral sheets. PMID:26151150

  10. Reducible cationic lipids for gene transfer.

    PubMed Central

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

    2001-01-01

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

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

    PubMed

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

    2016-07-21

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

  12. Where do those remains come from?

    PubMed

    Nociarová, Dominika; Adserias, M Jose; Malgosa, Assumpció; Galtés, Ignasi

    2014-12-01

    Part of the study of skeletal remains or corpses in advance decay located in the field involves determining their origin. They may be the result of criminal activity, accident, unearthed because of erosion, or they may also have originated from a cemetery. The discovery site, condition of the remains, and the associated artifacts, are factors that could be helpful for the forensic anthropologist to identify the origin of the remains. In order to contribute to this recognition, an analysis was made of the exhumations of 168 unclaimed human remains from the cemetery of Terrassa (Catalonia, Spain). This investigation presents a description of artifacts and conditions of remains that could indicate that the human remains may have originated from a cemetery. PMID:25459276

  13. Method for the safe disposal of alkali metal

    DOEpatents

    Johnson, Terry R.

    1977-01-01

    Alkali metals such as those employed in liquid metal coolant systems can be safely reacted to form hydroxides by first dissolving the alkali metal in relatively inert metals such as lead or bismuth. The alloy thus formed is contacted with a molten salt including the alkali metal hydroxide and possibly the alkali metal carbonate in the presence of oxygen. This oxidizes the alkali metal to an oxide which is soluble within the molten salt. The salt is separated and contacted with steam or steam-CO.sub.2 mixture to convert the alkali metal oxide to the hydroxide. These reactions can be conducted with minimal hydrogen evolution and with the heat of reaction distributed between the several reaction steps.

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

    PubMed

    Rao, N Madhusudhana

    2010-03-01

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

  15. Determination of the common and rare alkalies in mineral analysis

    USGS Publications Warehouse

    Wells, R.C.; Stevens, R.E.

    1934-01-01

    Methods are described which afford a determination of each member of the alkali group and are successful in dealing with the quantities of the rare alkalies found in rocks and minerals. The procedures are relatively rapid and based chiefly on the use of chloroplatinic acid, absolute alcohol and ether, and ammonium sulfate. The percentages of all the alkalies found in a number of minerals are given.

  16. Environmental mercury contamination around a chlor-alkali plant

    SciTech Connect

    Lodenius, M.; Tulisalo, E.

    1984-04-01

    The chlor-alkali industry is one of the most important emitters of mercury. This metal is effectively spread from chlor-alkali plants into the atmosphere and it has been reported that only a few percent of the mercury emissions are deposited locally the major part spreading over very large areas. The purpose of this investigation was to study the spreading of mercury up to 100 km from a chlor-alkali plant using three different biological indicators.

  17. Electrochemical devices utilizing molten alkali metal electrode-reactant

    DOEpatents

    Hitchcock, D.C.; Mailhe, C.C.; De Jonghe, L.C.

    1985-07-10

    Electrochemical cells are provided with a reactive metal to reduce the oxide of the alkali metal electrode-reactant. Cells employing a molten alkali metal electrode, e.g., sodium, in contact with a ceramic electrolyte, which is a conductor of the ions of the alkali metal forming the electrode, exhibit a lower resistance when a reactive metal, e.g., vanadium, is allowed to react with and reduce the alkali metal oxide. Such cells exhibit less degradation of the electrolyte and of the glass seals often used to joining the electrolyte to the other components of the cell under cycling conditions.

  18. Electrochemical devices utilizing molten alkali metal electrode-reactant

    DOEpatents

    Hitchcock, David C.; Mailhe, Catherine C.; De Jonghe, Lutgard C.

    1986-01-01

    Electrochemical cells are provided with a reactive metal to reduce the oxide of the alkali metal electrode-reactant. Cells employing a molten alkali metal electrode, e.g., sodium, in contact with a ceramic electrolyte, which is a conductor of the ions of the alkali metal forming the electrode, exhibit a lower resistance when a reactive metal, e.g., vanadium, is allowed to react with and reduce the alkali metal oxide. Such cells exhibit less degradation of the electrolyte and of the glass seals often used to joining the electrolyte to the other components of the cell under cycling conditions.

  19. High cation transport polymer electrolyte

    DOEpatents

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

    2007-06-05

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

  20. Alkali Metal Ion Complexes with Phosphates, Nucleotides, Amino Acids, and Related Ligands of Biological Relevance. Their Properties in Solution.

    PubMed

    Crea, Francesco; De Stefano, Concetta; Foti, Claudia; Lando, Gabriele; Milea, Demetrio; Sammartano, Silvio

    2016-01-01

    Alkali metal ions play very important roles in all biological systems, some of them are essential for life. Their concentration depends on several physiological factors and is very variable. For example, sodium concentrations in human fluids vary from quite low (e.g., 8.2 mmol dm(-3) in mature maternal milk) to high values (0.14 mol dm(-3) in blood plasma). While many data on the concentration of Na(+) and K(+) in various fluids are available, the information on other alkali metal cations is scarce. Since many vital functions depend on the network of interactions occurring in various biofluids, this chapter reviews their complex formation with phosphates, nucleotides, amino acids, and related ligands of biological relevance. Literature data on this topic are quite rare if compared to other cations. Generally, the stability of alkali metal ion complexes of organic and inorganic ligands is rather low (usually log K < 2) and depends on the charge of the ligand, owing to the ionic nature of the interactions. At the same time, the size of the cation is an important factor that influences the stability: very often, but not always (e.g., for sulfate), it follows the trend Li(+) > Na(+) > K(+) > Rb(+) > Cs(+). For example, for citrate it is: log K ML = 0.88, 0.80, 0.48, 0.38, and 0.13 at 25 °C and infinite dilution. Some considerations are made on the main aspects related to the difficulties in the determination of weak complexes. The importance of the alkali metal ion complexes was also studied in the light of modelling natural fluids and in the use of these cations as probes for different processes. Some empirical relationships are proposed for the dependence of the stability constants of Na(+) complexes on the ligand charge, as well as for correlations among log K values of NaL, KL or LiL species (L = generic ligand). PMID:26860301

  1. Star-like superalkali cations featuring planar pentacoordinate carbon

    NASA Astrophysics Data System (ADS)

    Guo, Jin-Chang; Tian, Wen-Juan; Wang, Ying-Jin; Zhao, Xue-Feng; Wu, Yan-Bo; Zhai, Hua-Jin; Li, Si-Dian

    2016-06-01

    Superalkali cations, known to possess low vertical electron affinities (VEAs), high vertical detachment energies, and large highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gaps, are intriguing chemical species. Thermodynamically, such species need to be the global minima in order to serve as the promising targets for experimental realization. In this work, we propose the strategies of polyhalogenation and polyalkalination for designing the superalkali cations. By applying these strategies, the local-minimum planar pentacoordinate carbon (ppC) cluster CBe5 can be modified to form a series of star-like superalkali ppC or quasi-ppC CBe5X5+ (X = F, Cl, Br, Li, Na, K) cations containing a CBe5 moiety. Polyhalogenation and polyalkalination on the CBe5 unit may help eliminate the high reactivity of bare CBe5 molecule by covering the reactive Be atoms with noble halogen anions and alkali cations. Computational exploration of the potential energy surfaces reveals that the star-like ppC or quasi-ppC CBe5X5+ (X = F, Cl, Br, Li, Na, K) clusters are the true global minima of the systems. The predicted VEAs for CBe5X5+ range from 3.01 to 3.71 eV for X = F, Cl, Br and 2.12-2.51 eV for X = Li, Na, K, being below the lower bound of the atomic ionization potential of 3.89 eV in the periodic table. Large HOMO-LUMO energy gaps are also revealed for the species: 10.76-11.07 eV for X = F, Cl, Br and 4.99-6.91 eV for X = Li, Na, K. These designer clusters represent the first series of superalkali cations with a ppC center. Bonding analyses show five Be-X-Be three-center two-electron (3c-2e) σ bonds for the peripheral bonding, whereas the central C atom is associated with one 6c-2e π bond and three 6c-2e σ bonds, rendering (π and σ) double aromaticity. Born-Oppenheimer molecular dynamics simulations indicate that the CBe5 motif is robust in the clusters. As planar hypercoordination carbon species are often thermodynamically unstable and

  2. Star-like superalkali cations featuring planar pentacoordinate carbon.

    PubMed

    Guo, Jin-Chang; Tian, Wen-Juan; Wang, Ying-Jin; Zhao, Xue-Feng; Wu, Yan-Bo; Zhai, Hua-Jin; Li, Si-Dian

    2016-06-28

    Superalkali cations, known to possess low vertical electron affinities (VEAs), high vertical detachment energies, and large highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gaps, are intriguing chemical species. Thermodynamically, such species need to be the global minima in order to serve as the promising targets for experimental realization. In this work, we propose the strategies of polyhalogenation and polyalkalination for designing the superalkali cations. By applying these strategies, the local-minimum planar pentacoordinate carbon (ppC) cluster CBe5 can be modified to form a series of star-like superalkali ppC or quasi-ppC CBe5X5 (+) (X = F, Cl, Br, Li, Na, K) cations containing a CBe5 moiety. Polyhalogenation and polyalkalination on the CBe5 unit may help eliminate the high reactivity of bare CBe5 molecule by covering the reactive Be atoms with noble halogen anions and alkali cations. Computational exploration of the potential energy surfaces reveals that the star-like ppC or quasi-ppC CBe5X5 (+) (X = F, Cl, Br, Li, Na, K) clusters are the true global minima of the systems. The predicted VEAs for CBe5X5 (+) range from 3.01 to 3.71 eV for X = F, Cl, Br and 2.12-2.51 eV for X = Li, Na, K, being below the lower bound of the atomic ionization potential of 3.89 eV in the periodic table. Large HOMO-LUMO energy gaps are also revealed for the species: 10.76-11.07 eV for X = F, Cl, Br and 4.99-6.91 eV for X = Li, Na, K. These designer clusters represent the first series of superalkali cations with a ppC center. Bonding analyses show five Be-X-Be three-center two-electron (3c-2e) σ bonds for the peripheral bonding, whereas the central C atom is associated with one 6c-2e π bond and three 6c-2e σ bonds, rendering (π and σ) double aromaticity. Born-Oppenheimer molecular dynamics simulations indicate that the CBe5 motif is robust in the clusters. As planar hypercoordination carbon species are often thermodynamically

  3. Electrodes For Alkali-Metal Thermoelectric Converters

    NASA Technical Reports Server (NTRS)

    Williams, Roger M.; Wheeler, Bob L.; Jeffries-Nakamura, Barbara; Lamb, James L.; Bankston, C. Perry; Cole, Terry

    1989-01-01

    Combination of thin, porous electrode and overlying collector grid reduces internal resistance of alkali-metal thermoelectric converter cell. Low resistance of new electrode and grid boosts power density nearly to 1 W/cm2 of electrode area at typical operating temperatures of 1,000 to 1,300 K. Conductive grid encircles electrode film on alumina tube. Bus wire runs along tube to collect electrical current from grid. Such converters used to transform solar, nuclear, and waste heat into electric power.

  4. High power diode pumped alkali vapor lasers

    NASA Astrophysics Data System (ADS)

    Zweiback, J.; Krupke, B.

    2008-05-01

    Diode pumped alkali lasers have developed rapidly since their first demonstration. These lasers offer a path to convert highly efficient, but relatively low brightness, laser diodes into a single high power, high brightness beam. General Atomics has been engaged in the development of DPALs with scalable architectures. We have examined different species and pump characteristics. We show that high absorption can be achieved even when the pump source bandwidth is several times the absorption bandwidth. In addition, we present experimental results for both potassium and rubidium systems pumped with a 0.2 nm bandwidth alexandrite laser. These data show slope efficiencies of 67% and 72% respectively.

  5. Cathode architectures for alkali metal / oxygen batteries

    SciTech Connect

    Visco, Steven J; Nimon, Vitaliy; De Jonghe, Lutgard C; Volfkovich, Yury; Bograchev, Daniil

    2015-01-13

    Electrochemical energy storage devices, such as alkali metal-oxygen battery cells (e.g., non-aqueous lithium-air cells), have a cathode architecture with a porous structure and pore composition that is tailored to improve cell performance, especially as it pertains to one or more of the discharge/charge rate, cycle life, and delivered ampere-hour capacity. A porous cathode architecture having a pore volume that is derived from pores of varying radii wherein the pore size distribution is tailored as a function of the architecture thickness is one way to achieve one or more of the aforementioned cell performance improvements.

  6. Elucidation of transport mechanism and enhanced alkali ion transference numbers in mixed alkali metal-organic ionic molten salts.

    PubMed

    Chen, Fangfang; Forsyth, Maria

    2016-07-28

    Mixed salts of Ionic Liquids (ILs) and alkali metal salts, developed as electrolytes for lithium and sodium batteries, have shown a remarkable ability to facilitate high rate capability for lithium and sodium electrochemical cycling. It has been suggested that this may be due to a high alkali metal ion transference number at concentrations approaching 50 mol% Li(+) or Na(+), relative to lower concentrations. Computational investigations for two IL systems illustrate the formation of extended alkali-anion aggregates as the alkali metal ion concentration increases. This tends to favor the diffusion of alkali metal ions compared with other ionic species in electrolyte solutions; behavior that has recently been reported for Li(+) in a phosphonium ionic liquid, thus an increasing alkali transference number. The mechanism of alkali metal ion diffusion via this extended coordination environment present at high concentrations is explained and compared to the dynamics at lower concentrations. Heterogeneous alkali metal ion dynamics are also evident and, somewhat counter-intuitively, it appears that the faster ions are those that are generally found clustered with the anions. Furthermore these fast alkali metal ions appear to correlate with fastest ionic liquid solvent ions. PMID:27375042

  7. Toys Remain Viral Playground for 24 Hours

    MedlinePlus

    ... a toy's surface at typical indoor temperatures and humidity levels. Specifically, they tested the ability of so- ... East Respiratory Syndrome (MERS). At 60 percent relative humidity, 1 percent of the virus remained infectious on ...

  8. 'Doubly Magic' Conditions in Magic-Wavelength Trapping of Ultracold Alkali-Metal Atoms

    SciTech Connect

    Derevianko, Andrei

    2010-07-16

    In experiments with trapped atoms, atomic energy levels are shifted by the trapping optical and magnetic fields. Regardless of this strong perturbation, precision spectroscopy may be still carried out using specially crafted, 'magic' trapping fields. Finding these conditions for particularly valuable microwave transitions in alkali-metal atoms has so far remained an open challenge. Here I demonstrate that the microwave transitions in alkali-metal atoms may be indeed made impervious to both trapping laser intensity and fluctuations of magnetic fields. I consider driving multiphoton transitions between the clock levels and show that these 'doubly magic' conditions are realized at special values of trapping laser wavelengths and fixed values of relatively weak magnetic fields. This finding has implications for precision measurements and quantum information processing with qubits stored in hyperfine manifolds.

  9. Cation Diffusion in Xenotime

    NASA Astrophysics Data System (ADS)

    Cherniak, D. J.

    2004-05-01

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

  10. Superconductivity in alkali metal intercalated iron selenides.

    PubMed

    Krzton-Maziopa, A; Svitlyk, V; Pomjakushina, E; Puzniak, R; Conder, K

    2016-07-27

    Alkali metal intercalated iron selenide superconductors A x Fe2-y Se2 (where A  =  K, Rb, Cs, Tl/K, and Tl/Rb) are characterized by several unique properties, which were not revealed in other superconducting materials. The compounds crystallize in overall simple layered structure with FeSe layers intercalated with alkali metal. The structure turned out to be pretty complex as the existing Fe-vacancies order below ~550 K, which further leads to an antiferromagnetic ordering with Néel temperature fairly above room temperature. At even lower temperatures a phase separation is observed. While one of these phases stays magnetic down to the lowest temperatures the second is becoming superconducting below ~30 K. All these effects give rise to complex relationships between the structure, magnetism and superconductivity. In particular the iron vacancy ordering, linked with a long-range magnetic order and a mesoscopic phase separation, is assumed to be an intrinsic property of the system. Since the discovery of superconductivity in those compounds in 2010 they were investigated very extensively. Results of the studies conducted using a variety of experimental techniques and performed during the last five years were published in hundreds of reports. The present paper reviews scientific work concerning methods of synthesis and crystal growth, structural and superconducting properties as well as pressure investigations. PMID:27248118

  11. Durability of Alkali Activated Blast Furnace Slag

    NASA Astrophysics Data System (ADS)

    Ellis, K.; Alharbi, N.; Matheu, P. S.; Varela, B.; Hailstone, R.

    2015-11-01

    The alkali activation of blast furnace slag has the potential to reduce the environmental impact of cementitious materials and to be applied in geographic zones where weather is a factor that negatively affects performance of materials based on Ordinary Portland Cement. The scientific literature provides many examples of alkali activated slag with high compressive strengths; however research into the durability and resistance to aggressive environments is still necessary for applications in harsh weather conditions. In this study two design mixes of blast furnace slag with mine tailings were activated with a potassium based solution. The design mixes were characterized by scanning electron microscopy, BET analysis and compressive strength testing. Freeze-thaw testing up to 100 freeze-thaw cycles was performed in 10% road salt solution. Our findings included compressive strength of up to 100 MPa after 28 days of curing and 120 MPa after freeze-thaw testing. The relationship between pore size, compressive strength, and compressive strength after freeze-thaw was explored.

  12. Superconductivity in alkali metal intercalated iron selenides

    NASA Astrophysics Data System (ADS)

    Krzton-Maziopa, A.; Svitlyk, V.; Pomjakushina, E.; Puzniak, R.; Conder, K.

    2016-07-01

    Alkali metal intercalated iron selenide superconductors A x Fe2‑y Se2 (where A  =  K, Rb, Cs, Tl/K, and Tl/Rb) are characterized by several unique properties, which were not revealed in other superconducting materials. The compounds crystallize in overall simple layered structure with FeSe layers intercalated with alkali metal. The structure turned out to be pretty complex as the existing Fe-vacancies order below ~550 K, which further leads to an antiferromagnetic ordering with Néel temperature fairly above room temperature. At even lower temperatures a phase separation is observed. While one of these phases stays magnetic down to the lowest temperatures the second is becoming superconducting below ~30 K. All these effects give rise to complex relationships between the structure, magnetism and superconductivity. In particular the iron vacancy ordering, linked with a long-range magnetic order and a mesoscopic phase separation, is assumed to be an intrinsic property of the system. Since the discovery of superconductivity in those compounds in 2010 they were investigated very extensively. Results of the studies conducted using a variety of experimental techniques and performed during the last five years were published in hundreds of reports. The present paper reviews scientific work concerning methods of synthesis and crystal growth, structural and superconducting properties as well as pressure investigations.

  13. Unconventional Superconductivity of Alkali-doped Fullerenes

    NASA Astrophysics Data System (ADS)

    Potocnik, Anton; Krajnc, Andraz; Jeglic, Peter; Prassides, Kosmas; Rosseinsky, Matthew J.; Arcon, Denis

    2014-03-01

    The superconductivity of the alkali-doped fullerenes (A3C60, A = alkali metal) has been so far discussed within the standard theory of superconductivity developed by Bardeen, Cooper and Shrieffer (BCS), even thought, they exhibit relatively high critical temperatures (up to Tc = 32 K). However, after our recent high-pressure measurements on Cs3C60 such description became questionable. We have shown that the superconducting phase of A3C60, in fact, borders the antiferromagnetic insulating phase (AFI), commonly observed for high-temperature superconductors like cuprates or pnictides. In addition, we also increased the maximal Tc to 38 K. To investigate this peculiar superconductivity close to the border with AFI state we employed nuclear magnetic resonance technique on Cs3-xRbxC60 and on Cs3C60 at various high pressures. Our results could not be correctly explained either by the standard BCS or the extended BCS that includes electron-electron repulsion interaction - the Migdal-Eliashberg theory. Far better agreement is obtained by the Dynamical Mean Field Theory. Due to similarity with other unconventional superconductors these results could also be relevant to other unconventional high-temperature superconductors.

  14. Decalcification resistance of alkali-activated slag.

    PubMed

    Komljenović, Miroslav M; Baščarević, Zvezdana; Marjanović, Nataša; Nikolić, Violeta

    2012-09-30

    This paper analyses the effects of decalcification in concentrated 6M NH(4)NO(3) solution on mechanical and microstructural properties of alkali-activated slag (AAS). Portland-slag cement (CEM II/A-S 42.5 N) was used as a benchmark material. Decalcification process led to a decrease in strength, both in AAS and in CEM II, and this effect was more pronounced in CEM II. The decrease in strength was explicitly related to the decrease in Ca/Si atomic ratio of C-S-H gel. A very low ratio of Ca/Si ~0.3 in AAS was the consequence of coexistence of C-S-H(I) gel and silica gel. During decalcification of AAS almost complete leaching of sodium and tetrahedral aluminum from C-S-H(I) gel also took place. AAS showed significantly higher resistance to decalcification in relation to the benchmark CEM II due to the absence of portlandite, high level of polymerization of silicate chains, low level of aluminum for silicon substitution in the structure of C-S-H(I), and the formation of protective layer of polymerized silica gel during decalcification process. In stabilization/solidification processes alkali-activated slag represents a more promising solution than Portland-slag cement due to significantly higher resistance to decalcification. PMID:22818592

  15. Dynamics of reactive ultracold alkali polar molecules

    NASA Astrophysics Data System (ADS)

    Quéméner, Goulven; Bohn, John; Petrov, Alexander; Kotochigova, Svetlana

    2011-05-01

    Recently, ultracold polar molecules of KRb have been created. These molecules are chemically reactive and their lifetime in a trap is limited. However, their lifetime increases when they are loaded into a 1D optical lattice in the presence of an electric field. These results naturally raise the question of manipulating ultracold collisions of other species of alkali dimer molecules, with an eye toward both novel stereochemistry, as well as suppressing unwanted reactions, to enable condensed matter applications. In this talk, we report on a comparative study between the bi-alkali polar molecules of LiNa, LiK, LiRb, LiCs which have been predicted to be reactive. We compute the isotropic C6 coefficients of these systems and we predict the elastic and reactive rate coefficients when an electric field is applied in a 1D optical lattice. We will discuss the efficacy of evaporative cooling for each species. This work was supported by a MURI-AFOSR grant.

  16. Lithium tracer-diffusion in an alkali-basaltic melt — An ion-microprobe determination

    NASA Astrophysics Data System (ADS)

    Lowry, R. K.; Reed, S. J. B.; Nolan, J.; Henderson, P.; Long, J. V. P.

    1981-03-01

    An ion-microprobe-based technique has been used to measure lithium tracer-diffusion coefficients ( D Li) in an alkali-basaltic melt at 1300, 1350 and 1400°C. The results can be expressed in the form: D Li=7.5 ×10 -2exp(-27,600/RT)cm 2S -1 The results show significantly faster diffusion rates than those previously recorded for other monovalent, divalent and trivalent cations in a tholeiitic melt. Consequently, diffusive transport of ions acting over a given time in a basaltic melt can produce a wider range of transport distance values than hitherto supposed. Hence, it is concluded that great care should be exercised when applying diffusion data to petrological problems.

  17. Fluorescent probes and bioimaging: alkali metals, alkaline earth metals and pH.

    PubMed

    Yin, Jun; Hu, Ying; Yoon, Juyoung

    2015-07-21

    All living species and life forms have an absolute requirement for bio-functional metals and acid-base equilibrium chemistry owing to the critical roles they play in biological processes. Hence, a great need exists for efficient methods to detect and monitor biometals and acids. In the last few years, great attention has been paid to the development of organic molecule based fluorescent chemosensors. The availability of new synthetic fluorescent probes has made fluorescence microscopy an indispensable tool for tracing biologically important molecules and in the area of clinical diagnostics. This review highlights the recent advances that have been made in the design and bioimaging applications of fluorescent probes for alkali metals and alkaline earth metal cations, including lithium, sodium and potassium, magnesium and calcium, and for pH determination within biological systems. PMID:25317749

  18. Low-frequency dynamics of aqueous alkali chloride solutions as probed by terahertz spectroscopy

    NASA Astrophysics Data System (ADS)

    Kann, Z. R.; Skinner, J. L.

    2016-06-01

    Terahertz (far infrared) spectroscopy provides a useful tool for probing both ionic motions in solution and the effect of ionic solutes on the dynamics of the solvent. In this study, we calculate terahertz spectra of aqueous alkali chloride solutions using classical but novel (the water model includes three-body interactions, the ion parameterization is non-standard, and the dipole surface is polarizable) molecular dynamics simulations. The calculated spectra compare reasonably well to experimental spectra. Decomposition of the calculated spectra is used to gain a deeper understanding of the physical phenomena underlying the spectra and the connection to, for instance, the vibrational density of states for the ions. The decomposed results are also used to explain many of the cation-dependent trends observed in the experimental spectra.

  19. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., alkali salt. 721.8900 Section 721.8900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.8900 Substituted halogenated pyridinol, alkali salt. (a) Chemical..., chemical destruction and carbon adsorption. (iv) Release to water. Requirements as specified in § 721.90...

  20. Formation of lysinoalanine in egg white under alkali treatment.

    PubMed

    Zhao, Yan; Luo, Xuying; Li, Jianke; Xu, Mingsheng; Tu, Yonggang

    2016-03-01

    To investigate the formation mechanism of lysinoalanine (LAL) in eggs during the alkali treatment process, NaOH was used for the direct alkali treatment of egg white, ovalbumin, and amino acids; in addition, the amount of LAL formed during the alkali treatment process was measured. The results showed that the alkali treatment resulted in the formation of LAL in the egg white. The LAL content increased with increasing pH and temperature, with the LAL content first increasing and then leveling off with increasing time. The amount of LAL formed in the ovalbumin under the alkali treatment condition accounted for approximately 50.51% to 58.68% of the amount of LAL formed in the egg white. Thus, the LAL formed in the ovalbumin was the main source for the LAL in the egg white during the alkali treatment process. Under the alkali treatment condition, free L-serine, L-cysteine, and L-cystine reacted with L-lysine to form LAL; therefore, they are the precursor amino acids of LAL formed in eggs during the alkali treatment process. PMID:26772660

  1. Recovery of alkali metal constituents from catalytic coal conversion residues

    DOEpatents

    Soung, Wen Y.

    1984-01-01

    In a coal gasification operation (32) or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by contacting them (46, 53, 61, 69) with water or an aqueous solution to remove water-soluble alkali metal constituents and produce an aqueous solution enriched in said constituents. The aqueous solution thus produced is then contacted with carbon dioxide (63) to precipitate silicon constituents, the pH of the resultant solution is increased (81), preferably to a value in the range between about 12.5 and about 15.0, and the solution of increased pH is evaporated (84) to increase the alkali metal concentration. The concentrated aqueous solution is then recycled to the conversion process (86, 18, 17) where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

  2. 40 CFR 721.4740 - Alkali metal nitrites.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... defined in 40 CFR 721.3) containing amines. (b) ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkali metal nitrites. 721.4740... Substances § 721.4740 Alkali metal nitrites. (a) Chemical substances and significant new use subject...

  3. 40 CFR 721.4740 - Alkali metal nitrites.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... defined in 40 CFR 721.3) containing amines. (b) ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkali metal nitrites. 721.4740... Substances § 721.4740 Alkali metal nitrites. (a) Chemical substances and significant new use subject...

  4. 40 CFR 721.4740 - Alkali metal nitrites.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... defined in 40 CFR 721.3) containing amines. (b) ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkali metal nitrites. 721.4740... Substances § 721.4740 Alkali metal nitrites. (a) Chemical substances and significant new use subject...

  5. 40 CFR 721.4740 - Alkali metal nitrites.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... defined in 40 CFR 721.3) containing amines. (b) ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkali metal nitrites. 721.4740... Substances § 721.4740 Alkali metal nitrites. (a) Chemical substances and significant new use subject...

  6. Self-discharge in bimetallic cells containing alkali metal

    NASA Technical Reports Server (NTRS)

    Foster, M. S.; Hesson, J. C.; Shimotake, H.

    1969-01-01

    Theoretical analysis of thermally regenerative bimetallic cells with alkali metal anodes shows a relation between the current drawn and the rate of discharge under open-circuit conditions. The self-discharge rate of the cell is due to the dissolution and ionization of alkali metal atoms in the fused-salt electrolyte

  7. COMPLEX FLUORIDES OF PLUTONIUM AND AN ALKALI METAL

    DOEpatents

    Seaborg, G.T.

    1960-08-01

    A method is given for precipitating alkali metal plutonium fluorides. such as KPuF/sub 5/, KPu/sub 2/F/sub 9/, NaPuF/sub 5/, and RbPuF/sub 5/, from an aqueous plutonium(IV) solution by adding hydrogen fluoride and alkali-metal- fluoride.

  8. 40 CFR 721.4740 - Alkali metal nitrites.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.4740 Alkali metal nitrites. (a) Chemical substances and significant new use subject to reporting. (1) The category of chemical substances which are nitrites of the alkali metals (Group IA in...

  9. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkali metal alkyl...

  10. Potential energy curves via double electron-attachment calculations: Dissociation of alkali metal dimers

    NASA Astrophysics Data System (ADS)

    Musiał, Monika; Kowalska-Szojda, Katarzyna; Lyakh, Dmitry I.; Bartlett, Rodney J.

    2013-05-01

    The recently developed method [M. Musiał, J. Chem. Phys. 136, 134111 (2012), 10.1063/1.3700438] to study double electron attached states has been applied to the description of the ground and excited state potential energy curves of the alkali metal dimers. The method is based on the multireference coupled cluster scheme formulated within the Fock space formalism for the (2,0) sector. Due to the use of the efficient intermediate Hamiltonian formulation, the approach is free from the intruder states problem. The description of the neutral alkali metal dimers is accomplished via attaching two electrons to the corresponding doubly ionized system. This way is particularly advantageous when a closed shell molecule dissociates into open shell subunits while its doubly positive cation generates the closed shell fragments. In the current work, we generate the potential energy curves for the ground and multiple excited states of the Li2 and Na2 molecules. In all cases the potential energy curves are smooth for the entire range of interatomic distances (from the equilibrium point to the dissociation limit). Based on the calculated potential energy curves, we are able to compute spectroscopic parameters of the systems studied.

  11. Molecular dispersion energy parameters for alkali and halide ions in aqueous solution.

    PubMed

    Reiser, S; Deublein, S; Vrabec, J; Hasse, H

    2014-01-28

    Thermodynamic properties of aqueous solutions containing alkali and halide ions are determined by molecular simulation. The following ions are studied: Li(+), Na(+), K(+), Rb(+), Cs(+), F(-), Cl(-), Br(-), and I(-). The employed ion force fields consist of one Lennard-Jones (LJ) site and one concentric point charge with a magnitude of ±1 e. The SPC/E model is used for water. The LJ size parameter of the ion models is taken from Deublein et al. [J. Chem. Phys. 136, 084501 (2012)], while the LJ energy parameter is determined in the present study based on experimental self-diffusion coefficient data of the alkali cations and the halide anions in aqueous solutions as well as the position of the first maximum of the radial distribution function of water around the ions. On the basis of these force field parameters, the electric conductivity, the hydration dynamics of water molecules around the ions, and the enthalpy of hydration is predicted. Considering a wide range of salinity, this study is conducted at temperatures of 293.15 and 298.15 K and a pressure of 1 bar. PMID:25669552

  12. Alkali metal control over N-N cleavage in iron complexes.

    PubMed

    Grubel, Katarzyna; Brennessel, William W; Mercado, Brandon Q; Holland, Patrick L

    2014-12-01

    Though N2 cleavage on K-promoted Fe surfaces is important in the large-scale Haber-Bosch process, there is still ambiguity about the number of Fe atoms involved during the N-N cleaving step and the interactions responsible for the promoting ability of K. This work explores a molecular Fe system for N2 reduction, particularly focusing on the differences in the results obtained using different alkali metals as reductants (Na, K, Rb, Cs). The products of these reactions feature new types of Fe-N2 and Fe-nitride cores. Surprisingly, adding more equivalents of reductant to the system gives a product in which the N-N bond is not cleaved, indicating that the reducing power is not the most important factor that determines the extent of N2 activation. On the other hand, the results suggest that the size of the alkali metal cation can control the number of Fe atoms that can approach N2, which in turn controls the ability to achieve N2 cleavage. The accumulated results indicate that cleaving the triple N-N bond to nitrides is facilitated by simultaneous approach of least three low-valent Fe atoms to a single molecule of N2. PMID:25412468

  13. Molecular dispersion energy parameters for alkali and halide ions in aqueous solution

    SciTech Connect

    Reiser, S.; Deublein, S.; Hasse, H.; Vrabec, J.

    2014-01-28

    Thermodynamic properties of aqueous solutions containing alkali and halide ions are determined by molecular simulation. The following ions are studied: Li{sup +}, Na{sup +}, K{sup +}, Rb{sup +}, Cs{sup +}, F{sup −}, Cl{sup −}, Br{sup −}, and I{sup −}. The employed ion force fields consist of one Lennard-Jones (LJ) site and one concentric point charge with a magnitude of ±1 e. The SPC/E model is used for water. The LJ size parameter of the ion models is taken from Deublein et al. [J. Chem. Phys. 136, 084501 (2012)], while the LJ energy parameter is determined in the present study based on experimental self-diffusion coefficient data of the alkali cations and the halide anions in aqueous solutions as well as the position of the first maximum of the radial distribution function of water around the ions. On the basis of these force field parameters, the electric conductivity, the hydration dynamics of water molecules around the ions, and the enthalpy of hydration is predicted. Considering a wide range of salinity, this study is conducted at temperatures of 293.15 and 298.15 K and a pressure of 1 bar.

  14. The fate of minor alkali elements in the chemical evolution of salt lakes

    PubMed Central

    2011-01-01

    Alkaline earth elements and alkali metals (Mg, Ca, Na and K) play an important role in the geochemical evolution of saline lakes as the final brine type is defined by the abundance of these elements. The role of major ions in brine evolution has been studied in great detail, but little has been done to investigate the behaviour of minor alkali elements in these systems despite their similar chemical affinities to the major cations. We have examined three major anionic brine types, chloride, sulphate, and bicarbonate-carbonate, in fifteen lakes in North America and Antarctica to determine the geochemical behaviour of lithium, rubidium, strontium, and barium. Lithium and rubidium are largely conservative in all water types, and their concentrations are the result of long-term solute input and concentration through evaporation and/or sublimation. Strontium and barium behaviours vary with anionic brine type. Strontium can be removed in sulphate and carbonate-rich lakes by the precipitation of carbonate minerals. Barium may be removed in chloride and sulphate brines by either the precipitation of barite and perhaps biological uptake. PMID:21992434

  15. Alkali and transition metal (Ag, Cu) salts of bridged 5-nitrotetrazole derivatives for energetic applications.

    PubMed

    Klapötke, Thomas M; Sabaté, Carles Miró; Rasp, Matthias

    2009-03-14

    A family of energetic salts based on the novel 5-(5-nitrotetrazole-2-ylmethyl)-tetrazolate anion (NTTz(-)) with alkali metals (Li(+), Na(+), K(+), Rb(+) and Cs(+)) were synthesized by the reaction of the free acid 5-(5-nitrotetrazole-2-ylmethyl)-tetrazole with a suitable alkali metal base (bicarbonate or carbonate) in alcohol or water. The sodium salt () was, in turn, used to form salts containing the NTTz(-) anion and Ag(+) () or Cu(2+) (, and ) cations. The new compounds were characterized by IR, Raman and NMR spectroscopy, mass spectroscopy, elemental analysis and differential scanning calorimetry (DSC). In addition, the solid-state structure of the NTTz(-) anion was determined by diffraction methods using X-ray analysis. We also assessed the energetic properties of the compounds using standardized (BAM) tests. Interestingly, the silver and copper salts are easily and safely initiated by the laser beam generated by a Raman machine and some of the compounds reported here have promising properties for applications as a new class of nitrogen-rich, more environmentally-friendly energetic materials. PMID:19240918

  16. The fate of minor alkali elements in the chemical evolution of salt lakes.

    PubMed

    Witherow, Rebecca A; Lyons, W Berry

    2011-01-01

    Alkaline earth elements and alkali metals (Mg, Ca, Na and K) play an important role in the geochemical evolution of saline lakes as the final brine type is defined by the abundance of these elements. The role of major ions in brine evolution has been studied in great detail, but little has been done to investigate the behaviour of minor alkali elements in these systems despite their similar chemical affinities to the major cations. We have examined three major anionic brine types, chloride, sulphate, and bicarbonate-carbonate, in fifteen lakes in North America and Antarctica to determine the geochemical behaviour of lithium, rubidium, strontium, and barium. Lithium and rubidium are largely conservative in all water types, and their concentrations are the result of long-term solute input and concentration through evaporation and/or sublimation. Strontium and barium behaviours vary with anionic brine type. Strontium can be removed in sulphate and carbonate-rich lakes by the precipitation of carbonate minerals. Barium may be removed in chloride and sulphate brines by either the precipitation of barite and perhaps biological uptake. PMID:21992434

  17. Alkali Metal Control over N–N Cleavage in Iron Complexes

    PubMed Central

    2015-01-01

    Though N2 cleavage on K-promoted Fe surfaces is important in the large-scale Haber–Bosch process, there is still ambiguity about the number of Fe atoms involved during the N–N cleaving step and the interactions responsible for the promoting ability of K. This work explores a molecular Fe system for N2 reduction, particularly focusing on the differences in the results obtained using different alkali metals as reductants (Na, K, Rb, Cs). The products of these reactions feature new types of Fe–N2 and Fe-nitride cores. Surprisingly, adding more equivalents of reductant to the system gives a product in which the N–N bond is not cleaved, indicating that the reducing power is not the most important factor that determines the extent of N2 activation. On the other hand, the results suggest that the size of the alkali metal cation can control the number of Fe atoms that can approach N2, which in turn controls the ability to achieve N2 cleavage. The accumulated results indicate that cleaving the triple N–N bond to nitrides is facilitated by simultaneous approach of least three low-valent Fe atoms to a single molecule of N2. PMID:25412468

  18. Shallow electron traps in alkali halide crystals: Mollwo-Ivey relations of the optical absorption bands

    NASA Astrophysics Data System (ADS)

    Ziraps, Valters

    2001-03-01

    Evidences are given that two classes of the transient IR- absorption bands: (a) with max. at 0.27-0.36 eV in NaCl, KCl, KBr, KI and RbCl (due to shallow electron traps according G. Jacobs or due to bound polarons according E.V. Korovkin and T.A. Lebedkina) and (b) with max. at 0.15-0.36 eV in NaI, NaBr, NaCl:I, KCl:I, RbCl:I and RbBr:I (due to on-center STE localized at iodine dimer according M. Hirai and collaborators) are caused by the same defect- atomic alkali impurity center [M+]c0e- (electron e- trapped by a substitutional smaller size alkali cation impurity [M+]c0). The Mollwo-Ivey plots (for the transient IR-absorption bands) of the zero-phonon line energy E0 (for NaCl, KCl, KBr, RbCl and NaBr, KCl:I) and/or the low-energy edge valued E0 (for NaI, RbCl:I, RbBr:I) versus anion-cation distance (d) evidence that two types of the [M+]c0e- centers are predominant: (a) [Na+]c0e- in the KX and RbX host crystals with the relation E0approximately equals 6.15/d2.74, (b) [Li+]c03- in the NaX host crystals - E0approximately equals 29.4/d4.72. The Mollwo-Ivey relation E0approximately equals 18.36/d(superscript 2.70 is fulfilled as well for the F' band in NaCl, KCl, KBr, KI, RbCl, RbI if we use the F' center optical binding energy values E0.

  19. Effects of alkali treatments on Ag nanowire transparent conductive films

    NASA Astrophysics Data System (ADS)

    Kim, Sunho; Kang, Jun-gu; Eom, Tae-yil; Moon, Bongjin; Lee, Hoo-Jeong

    2016-06-01

    In this study, we employ various alkali materials (alkali metals with different base strengths, and ammonia gas and solution) to improve the conductivity of silver nanowire (Ag NW)-networked films. The alkali treatment appears to remove the surface oxide and improve the conductivity. When applied with TiO2 nanoparticles, the treatment appears more effective as the alkalis gather around wire junctions and help them weld to each other via heat emitted from the reduction reaction. The ammonia solution treatment is found to be quick and aggressive, damaging the wires severely in the case of excessive treatment. On the other hand, the ammonia gas treatment seems much less aggressive and does not damage the wires even after a long exposure. The results of this study highlight the effectiveness of the alkali treatment in improving of the conductivity of Ag NW-networked transparent conductive films.

  20. Performance of Straight Steel Fibres Reinforced Alkali Activated Concrete

    NASA Astrophysics Data System (ADS)

    Faris, Meor Ahmad; Bakri Abdullah, Mohd Mustafa Al; Nizar Ismail, Khairul; Muniandy, Ratnasamy; Putra Jaya, Ramadhansyah

    2016-06-01

    This paper focus on the performance of alkali activated concrete produced by using fly ash activated by sodium silicate and sodium hydroxide solutions. These alkali activated concrete were reinforced with straight steel fibres with different weight percentage starting from 0 % up to 5 %. Chemical composition of raw material in the production alkali activated concrete which is fly ash was first identified by using X-ray fluorescence. Results reveal there have an effect of straight steel fibres inclusion to the alkali activated concrete. Highest compressive strength of alkali activated concrete which is 67.72 MPa was obtained when 3 % of straight fibres were added. As well as flexural strength, highest flexural strength which is 6.78 MPa was obtained at 3 % of straight steel fibres inclusions.

  1. Water and magmas: insights about the water solution mechanisms in alkali silicate melts from infrared, Raman, and 29Si solid-state NMR spectroscopies

    NASA Astrophysics Data System (ADS)

    Le Losq, Charles; Mysen, Bjorn O.; Cody, George D.

    2015-12-01

    Degassing of water during the ascent of hydrous magma in a volcanic edifice produces dramatic changes in the magma density and viscosity. This can profoundly affect the dynamics of volcanic eruptions. The water exsolution history, in turn, is driven by the water solubility and solution mechanisms in the silicate melt. Previous studies pointed to dissolved water in silicate glasses and melts existing as molecules (H2Omol species) and hydroxyl groups, OH. These latter OH groups commonly are considered bonded to Si4+ but may form other bonds, such as with alkali or alkaline-earth cations, for instance. Those forms of bonding influence the structure of hydrous melts in different ways and, therefore, their properties. As a result, exsolution of water from magmas may have different eruptive consequences depending on the initial bonding mechanisms of the dissolved water. However, despite their importance, the solution mechanisms of water in silicate melts are not clear. In particular, how chemical composition of melts affects water solubility and solution mechanism is not well understood. In the present experimental study, components of such information are reported via determination of how water interacts with the cationic network of alkali (Li, Na, and K) silicate quenched melts. Results from 29Si single-pulse magic-angle spinning nuclear magnetic resonance (29Si SP MAS NMR), infrared, and Raman spectroscopies show that decreasing the ionic radius of alkali metal cation in silicate melts results in decreasing fraction of water dissolved as OH groups. The nature of OH bonding also changes as the alkali ionic radius changes. Therefore, as the speciation and bonding of water controls the degree of polymerization of melts, water will have different effects on the transport properties of silicate melts depending on their chemical composition. This conclusion, in turn, may affect volcanic phenomena related to the viscous relaxation of hydrous magmas, such as for instance the

  2. Cation effects on interfacial water organization of aqueous chloride solutions. I. Monovalent cations: Li+, Na+, K+, and NH4(+).

    PubMed

    Hua, Wei; Verreault, Dominique; Huang, Zishuai; Adams, Ellen M; Allen, Heather C

    2014-07-17

    The influence of monovalent cations on the interfacial water organization of alkali (LiCl, NaCl, and KCl) and ammonium chloride (NH4Cl) salt solutions was investigated using surface-sensitive conventional vibrational sum frequency generation (VSFG) and heterodyne-detected (HD-)VSFG spectroscopy. It was found in the conventional VSFG spectra that LiCl and NH4Cl significantly perturb water’s hydrogen-bonding network. In contrast, NaCl and KCl had little effect on the interfacial water structure and exhibited weak concentration dependency. The Im χs(2)(ωIR) spectra from HD-VSFG further revealed that, for all chloride solutions, the net transition dipole moments of hydrogen-bonded water molecules (O → H) are oriented more toward the vapor phase relative to neat water. This suggests the presence of an interfacial electric field generated from the formation of an ionic double layer in the interfacial region with a distribution of Cl(-) ions located above the countercations, in agreement with predictions from MD simulations. The magnitude of this electric field shows a small but definite cation specificity and follows the order Li(+) ≈ Na(+) > NH4(+) > K(+). The observed trend was found to be in good agreement with previously published surface potential data. PMID:24798506

  3. Cation Ordering in Layered Nickelates

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

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

  4. Liver targeting of catalase by cationization for prevention of acute liver failure in mice.

    PubMed

    Ma, Shen-Feng; Nishikawa, Makiya; Katsumi, Hidemasa; Yamashita, Fumiyoshi; Hashida, Mitsuru

    2006-01-10

    To achieve hepatic delivery of CAT for the prevention of CCl4-induced acute liver failure in mice, two types of cationized CAT derivatives, HMD- and ED-conjugated CAT, were developed. Slight structural changes occurred during cationization and the number of increased free amino groups was 3.1 in HMD-CAT and 13.6 in ED-CAT. 111In-cationized CAT derivatives showed an increased binding to HepG2 cells, and were rapidly taken up by the liver. H2O2-induced cytotoxicity in HepG2 cells was significantly prevented by preincubation of the cells with cationized CAT derivatives. A bolus intravenous injection of the cationized CAT derivatives reduced the hepatotoxicity induced by CCl4 in mice. The ED-CAT, which showed more rapid and greater binding to the liver than the HMD-CAT, exhibited more beneficial effects as far as all the parameters examined (serum GOT, GPT, LDH and hepatic GSH) were concerned, suggesting that a high degree of cationization is effective in delivering CAT to the liver to prevent CCl4-induced hepatotoxicity. These results suggest that cationized CAT derivatives are effective in preventing acute liver failure, and ED-based cationization is a suitable method for developing liver-targetable cationized CAT derivatives, because it provides CAT with a high degree of cationization and a high remaining enzymatic activity. PMID:16316705

  5. Catholic Identity Remains a Public Relations Asset

    ERIC Educational Resources Information Center

    Wirth, Eileen

    2004-01-01

    The massive sex scandal that rocked the Roman Catholic Church raises a question as to whether Catholic identity remains an asset that the nation's 8,000 Catholic schools should continue to promote. This case study found that continuing to promote Catholic identity has had no adverse effect on recruitment and enrollment at four Omaha, Nebraska,…

  6. Essential Qualities of Math Teaching Remain Unknown

    ERIC Educational Resources Information Center

    Cavanagh, Sean

    2008-01-01

    According to a new federal report, the qualities of an effective mathematics teacher remain frustratingly elusive. The report of the National Mathematics Advisory Panel does not show what college math content and coursework are most essential for teachers. While the report offered numerous conclusions about math curriculum, cognition, and…

  7. Juveniles' Motivations for Remaining in Prostitution

    ERIC Educational Resources Information Center

    Hwang, Shu-Ling; Bedford, Olwen

    2004-01-01

    Qualitative data from in-depth interviews were collected in 1990-1991, 1992, and 2000 with 49 prostituted juveniles remanded to two rehabilitation centers in Taiwan. These data are analyzed to explore Taiwanese prostituted juveniles' feelings about themselves and their work, their motivations for remaining in prostitution, and their difficulties…

  8. Odor analysis of decomposing buried human remains

    SciTech Connect

    Vass, Arpad Alexander; Smith, Rob R; Thompson, Cyril V; Burnett, Michael N; Dulgerian, Nishan; Eckenrode, Brian A

    2008-01-01

    This study, conducted at the University of Tennessee's Anthropological Research Facility (ARF), lists and ranks the primary chemical constituents which define the odor of decomposition of human remains as detected at the soil surface of shallow burial sites. Triple sorbent traps were used to collect air samples in the field and revealed eight major classes of chemicals which now contain 478 specific volatile compounds associated with burial decomposition. Samples were analyzed using gas chromatography-mass spectrometry (GC-MS) and were collected below and above the body, and at the soil surface of 1.5-3.5 ft. (0.46-1.07 m) deep burial sites of four individuals over a 4-year time span. New data were incorporated into the previously established Decompositional Odor Analysis (DOA) Database providing identification, chemical trends, and semi-quantitation of chemicals for evaluation. This research identifies the 'odor signatures' unique to the decomposition of buried human remains with projected ramifications on human remains detection canine training procedures and in the development of field portable analytical instruments which can be used to locate human remains in shallow burial sites.

  9. Elastic properties of alkali-feldspars

    NASA Astrophysics Data System (ADS)

    Waeselmann, N.; Brown, J.; Angel, R. J.; Ross, N.; Kaminsky, W.

    2013-12-01

    New measurements of single crystal elastic moduli for a suite of the alkali feldspars are reported. In order to interpret Earth's seismic structure, knowledge of the elastic properties of constituent minerals is essential. The elasticity of feldspar minerals, despite being the most abundant phase in Earth's crust (estimated to be more than 60%), were previously poorly characterized. All prior seismic and petrologic studies have utilized 50-year-old results, of questionable quality, based on 1-bar measurements on pseudo-single crystals. Alkali-feldspars present a large experimental challenge associated with their structural complexity. In the K-end member (KAlSi3O8) the symmetry is governed by Al/Si ordering, in the Na-end member (NaAlSi3O8) the symmetry is governed by whether or not there is a displacive collapse of the framework independent of the Al/Si ordering. K-feldspars exhibit monoclinic (C2/m) symmetry (necessitating determination of 13 elastic moduli) if disordered and triclinic (C-1) symmetry (21 elastic moduli) if ordered. Exsolution of Na-rich and K-rich phases is ubiquitous in natural samples, making it difficult to find suitable single phase and untwinned samples for study. The small single domain samples selected for this study were previously characterized by x-ray diffraction and microprobe analysis to ensure adequate sample quality. Surface wave velocities were measured on oriented surfaces of natural and synthetic single crystals using impulsively stimulated light scattering. A surface corrugation with a spacing of about 2 microns was impulsively created by the overlap of 100 ps infrared light pulses. The time evolution of the stimulated standing elastic waves was detected by measuring the intensity of diffraction from the surface corrugation of a variably delayed probe pulse. This method allows accurate (better than 0.2%) determination of velocities on samples smaller than 100 microns. The combination of measured surface wave velocities and

  10. Properties of alkali metal atoms deposited on a MgO surface: a systematic experimental and theoretical study.

    PubMed

    Finazzi, Emanuele; Di Valentin, Cristiana; Pacchioni, Gianfranco; Chiesa, Mario; Giamello, Elio; Gao, Hongjun; Lian, Jichun; Risse, Thomas; Freund, Hans-Joachim

    2008-01-01

    The adsorption of small amounts of alkali metal atoms (Li, Na, K, Rb, and Cs) on the surface of MgO powders and thin films has been studied by means of EPR spectroscopy and DFT calculations. From a comparison of the measured and computed g values and hyperfine coupling constants (hfccs), a tentative assignment of the preferred adsorption sites is proposed. All atoms bind preferentially to surface oxide anions, but the location of these anions differs as a function of the deposition temperature and alkali metal. Lithium forms relatively strong bonds with MgO and can be stabilized at low temperatures on terrace sites. Potassium interacts very weakly with MgO and is stabilized only at specific sites, such as at reverse corners where it can interact simultaneously with three surface oxygen atoms (rubidium and cesium presumably behave in the same way). Sodium forms bonds of intermediate strength and could, in principle, populate more than a single site when deposited at room temperature. In all cases, large deviations of the hfccs from the gas-phase values are observed. These reductions in the hfccs are due to polarization effects and are not connected to ionization of the alkali metal, which would lead to the formation of an adsorbed cation and a trapped electron. In this respect, hydrogen atoms behave completely differently. Under similar conditions, they form (H(+))(e(-)) pairs. The reasons for this different behavior are discussed. PMID:18381711

  11. Impact of Alkali Source on Vitrification of SRS High Level Waste

    SciTech Connect

    LAMBERT, D. P.; MILLER, D. H.; PEELER, D. K.; SMITH, M. E.; STONE, M. E.

    2005-09-08

    can be reduced significantly by washing the solids to remove soluble species. The ''washing strategy'' for future sludge batches can be controlled to limit the soluble sodium remaining in the waste stream while balancing the alkali content of the frit to maintain acceptable glass properties as well as improve melter processing characteristics.

  12. Involvement of NADPH oxidases in alkali burn-induced corneal injury.

    PubMed

    Gu, Xue-Jun; Liu, Xian; Chen, Ying-Ying; Zhao, Yao; Xu, Man; Han, Xiao-Jian; Liu, Qiu-Ping; Yi, Jing-Lin; Li, Jing-Ming

    2016-07-01

    Chemical burns are a major cause of corneal injury. Oxidative stress, inflammatory responses and neovascularization after the chemical burn aggravate corneal damage, and lead to loss of vision. Although NADPH oxidases (Noxs) play a crucial role in the production of reactive oxygen species (ROS), the role of Noxs in chemical burn-induced corneal injury remains to be elucidated. In the present study, the transcription and expression of Noxs in corneas were examined by RT-qPCR, western blot analysis and immunofluorescence staining. It was found that alkali burns markedly upregulated the transcription and expression of Nox2 and Nox4 in human or mouse corneas. The inhibition of Noxs by diphenyleneiodonium (DPI) or apocynin (Apo) effectively attenuated alkali burn-induced ROS production and decreased 3-nitrotyrosine (3-NT) protein levels in the corneas. In addition, Noxs/CD11b double‑immunofluorescence staining indicated that Nox2 and Nox4 were partially co-localized with CD11b. DPI or Apo prevented the infiltration of CD11b-positive inflammatory cells, and inhibited the transcription of inflammatory cytokines following alkali burn-induced corneal injury. In our mouse model of alkali burn-induced corneal injury, corneal neovascularization (CNV) occurred on day 3, and it affected 50% of the whole area of the cornea on day 7, and on day 14, CNV coverage of the cornea reached maximum levels. DPI or Apo effectively attenuated alkali burn‑induced CNV and decreased the mRNA levels of angiogenic factors, including vascular endothelial growth factor (VEGF), VEGF receptors and matrix metalloproteinases (MMPs). Taken together, our data indicate that Noxs play a role in alkali burn-induced corneal injury by regulating oxidative stress, inflammatory responses and CNV, and we thus suggest that Noxs are a potential therapeutic target in the future treatment of chemical-induced corneal injury. PMID:27221536

  13. Solvent-averaged potentials for alkali-, earth alkali-, and alkylammonium halide aqueous solutions

    NASA Astrophysics Data System (ADS)

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

    2007-12-01

    We derive effective, solvent-free ion-ion potentials for alkali-, earth alkali-, and alkylammonium halide aqueous solutions. The implicit solvent potentials are parametrized to reproduce experimental osmotic coefficients. The modeling approach minimizes the amount of input required from atomistic (force field) models, which usually predict large variations in the effective ion-ion potentials at short distances. For the smaller ion species, the reported potentials are composed of a Coulomb and a Weeks-Chandler-Andersen term. For larger ions, we find that an additional, attractive potential is required at the contact minimum, which is related to solvent degrees of freedom that are usually not accounted for in standard electrostatics models. The reported potentials provide a simple and accurate force field for use in molecular dynamics and Monte Carlo simulations of (poly-)electrolyte systems.

  14. Volcanic Origin of Alkali Halides on Io

    NASA Technical Reports Server (NTRS)

    Schaefer, L.; Fegley, B., Jr.

    2003-01-01

    The recent observation of NaCl (gas) on Io confirms our earlier prediction that NaCl is produced volcanically. Here we extend our calculations by modeling thermochemical equilibrium of O, S, Li, Na, K, Rb, Cs, F, Cl, Br, and I as a function of temperature and pressure in a Pele-like volcanic gas with O/S/Na/Cl/K = 1.518/1/0.05/0.04/0.005 and CI chondritic ratios of the other (as yet unobserved) alkalis and halogens. For reference, the nominal temperature and pressure for Pele is 1760 plus or minus 210 K and 0.01 bars based on Galileo data and modeling.

  15. Alkali differentiation in LL-chondrites

    NASA Astrophysics Data System (ADS)

    Wlotzka, F.; Palme, H.; Spettel, B.; Wanke, H.; Fredriksson, K.; Noonan, A. F.

    1983-04-01

    The Kraehenberg and Bhola LL-group chondrites are heterogeneous agglomerates which contain a variety of lithic fragments and chondrules as well as crystal fragments. Both meteorites contain large, cm-sized fragments with high K enrichments. The K-rich inclusions are fragments of larger rock bodies which crystallized from melts of chondritic parent material that had previously been enriched in K and in heavier alkalies,while also being depleted in Na and metal. It is suggested that the K enrichment occurred as an exchange for Na in feldspars via a vapor phase, whose presence on the chondrite parent body (or bodies) is supported by the recent finding of fluid inclusions in chondritic silicates. Cooling rate considerations indicate that the K-rich rock units could not have been very large, implying that the K-rich materials were locally molten by, for example, impact.

  16. Heat pipes containing alkali metal working fluid

    NASA Technical Reports Server (NTRS)

    Morris, J. F. (Inventor)

    1981-01-01

    A technique for improving high temperature evaporation-condensation heat-transfer devices which have important and unique advantage in terrestrial and space energy processing is described. The device is in the form of a heat pipe comprising a sealed container or envelope which contains a capillary wick. The temperature of one end of the heat pipe is raised by the input of heat from an external heat source which is extremely hot and corrosive. A working fluid of a corrosive alkali metal, such as lithium, sodium, or potassium transfers this heat to a heat receiver remote from the heat source. The container and wick are fabricated from a superalloy containing a small percentage of a corrosion inhibiting or gettering element. Lanthanum, scandium, yttrium, thorium, and hafnium are utilized as the alloying metal.

  17. Comparative alkali washing of simulated radioactive sludge

    SciTech Connect

    Fugate, G.A.; Ensor, D.D.; Egan, B.Z.

    1996-10-01

    The treatment of large volumes of radioactive sludge generated from uranium and plutonium recovery processes is a pressing problem in the environmental restoration currently planned at various U.S. Department of Energy sites. This sludge, commonly stored in underground tanks, is mainly in the form of metal oxides or precipitated metal hydroxides and the bulk of this material is nonradioactive. One method being developed to pretreat this waste takes advantage of the amphoteric character of aluminum and other nonradioactive elements. Previous studies have reported on the dissolution of eleven elements from simulated sludge using NaOH solutions up to 6M. This work provides a comparative study using KOH. The effectiveness of the alkali washing as a treatment method to reduce the bulk of radioactive sludge requiring long term isolation will be discussed.

  18. Mill and the right to remain uninformed.

    PubMed

    Strasser, M

    1986-08-01

    In a recent article in the Journal of Medicine and Philosophy, David Ost (1984) claims that patients do not have a right to waive their right to information. He argues that patients cannot make informed rational decisions without full information and thus, a right to waive information would involve a right to avoid one's responsibility to act as an autonomous moral agent. In support of his position, Ost cites a passage from Mill. Yet, a correct interpretation of the passage in question would support one's right to remain uninformed in certain situations. If the information would hurt one's chances for survival or hurt one's ability to make calm, rational decisions, then one not only does not have a duty to find out the information, but one's exercising one's right to remain uninformed may be the only rational course of action to take. PMID:3540171

  19. Explosives remain preferred methods for platform abandonment

    SciTech Connect

    Pulsipher, A.; Daniel, W. IV; Kiesler, J.E.; Mackey, V. III

    1996-05-06

    Economics and safety concerns indicate that methods involving explosives remain the most practical and cost-effective means for abandoning oil and gas structures in the Gulf of Mexico. A decade has passed since 51 dead sea turtles, many endangered Kemp`s Ridleys, washed ashore on the Texas coast shortly after explosives helped remove several offshore platforms. Although no relationship between the explosions and the dead turtles was ever established, in response to widespread public concern, the US Minerals Management Service (MMS) and National Marine Fisheries Service (NMFS) implemented regulations limiting the size and timing of explosive charges. Also, more importantly, they required that operators pay for observers to survey waters surrounding platforms scheduled for removal for 48 hr before any detonations. If observers spot sea turtles or marine mammals within the danger zone, the platform abandonment is delayed until the turtles leave or are removed. However, concern about the effects of explosives on marine life remains.

  20. Solid state cell with alkali metal halo-alkali thiocyanate electrolyte

    SciTech Connect

    Rao, B. M.; Silbernagel, B. G.

    1980-02-26

    A novel electrochemical cell is disclosed utilizing: (A) an anode which contains an alkali metal as an anode-active material; (B) a cathode and (C) an electrolyte comprising an electrolytically effective amount of one or more compounds having the formula: (Ax)ma'scn wherein a is an alkali metal, X is a halogen, a' is an alkali metal and 0.1 < or = N < or = 10. Preferred systems include lithium-containing anodes, lithium-containing electrolytes and cathodes which contain cathode-active material selected from the group consisting of cathode-active sulfurs, halogens, halides, chromates, phosphates, oxides and chalcogenides, especially those chalcogenides of the empirical formula mzm wherein M is one or more metals selected from the group consisting of iron, titanium, zirconium, hafnium, niobium, tantalum and vanadium, Z is one or more chalcogens selected from the group consisting of oxygen, sulfur, selenium and tellurium, and M is a numerical value between about 1.8 and about 3.2.

  1. Ionic alkali halide XUV laser feasibility study

    SciTech Connect

    Yang, T.T.; Gylys, V.T.; Bower, R.D.; Harris, D.G.; Blauer, J.A.; Turner, C.E.; Hindy, R.N.

    1989-11-10

    The objective of this work is to assess the feasibility of a select set of ionic alkali halide XUV laser concepts by obtaining the relevant kinetic and spectroscopic parameters required for a proof-of-principle and conceptual design. The proposed lasers operate in the 80--200 nm spectral region and do not require input from outside radiation sources for their operation. Frequency up-conversion and frequency mixing techniques and therefore not considered in the work to be described. An experimental and theoretical study of a new type of laser operating in the extreme ultraviolet wavelength region has been conducted. The lasing species are singly ionized alkali halide molecules such as Rb{sup 2+}F{sub {minus}}, Rb{sup 2+}Br{sup {minus}} and Cs{sup 2+}F{sup {minus}}. These species are similar in electronic structure to the rare gas halide excimers, such as XeF and Krf, except that the ionic molecules emit at wavelengths of 80--200 nm, much shorter than the conventional rare-gas halide excimer laser. The radiative lifetime of these molecules are typically near 1 ns, which is about an order of magnitude shorter than that for rare-gas halide systems. The values of the cross section for stimulated emission are on the order of 1 {times} 10{sup {minus}16}cm{sup 2}. Because of the fundamental similarity to existing UV lasers, these systems show promise as a high power, efficient XUV lasers. 55 refs., 50 figs., 5 tabs.

  2. Remains of Comet-Shoemaker/Levy

    NASA Technical Reports Server (NTRS)

    2001-01-01

    This illustration of the Comet-Shoemaker/Levy collision shows the first piece of the remains of the comet crashing into Jupiter. This event occurred in 1994 after tidal forces from Jupiter caused the comet to break up into 21 separate pieces. Although on a very different scale, the physical mechanism for the breakup of Shoemaker/Levy also caused the tidal disruption of the star in RX J1242-11. (Illustration: SEDS/D. Seal (edited by CXC/M. Weiss)

  3. Polysaccharide Hydrogel Combined with Mesenchymal Stem Cells Promotes the Healing of Corneal Alkali Burn in Rats

    PubMed Central

    Liu, Xun; Yu, Min; Yang, Chunbo; Li, Xiaorong

    2015-01-01

    Corneal chemical burns are common ophthalmic injuries that may result in permanent visual impairment. Although significant advances have been achieved on the treatment of such cases, the structural and functional restoration of a chemical burn-injured cornea remains challenging. The applications of polysaccharide hydrogel and subconjunctival injection of mesenchymal stem cells (MSCs) have been reported to promote the healing of corneal wounds. In this study, polysaccharide was extracted from Hardy Orchid and mesenchymal stem cells (MSCs) were derived from Sprague-Dawley rats. Supplementation of the polysaccharide significantly enhanced the migration rate of primarily cultured rat corneal epithelial cells. We examined the therapeutic effects of polysaccharide in conjunction with MSCs application on the healing of corneal alkali burns in rats. Compared with either treatment alone, the combination strategy resulted in significantly better recovery of corneal epithelium and reduction in inflammation, neovascularization and opacity of healed cornea. Polysaccharide and MSCs acted additively to increase the expression of anti-inflammatory cytokine (TGF-β), antiangiogenic cytokine (TSP-1) and decrease those promoting inflammation (TNF-α), chemotaxis (MIP-1α and MCP-1) and angiogenesis (VEGF and MMP-2). This study provided evidence that Hardy Orchid derived polysaccharide and MSCs are safe and effective treatments for corneal alkali burns and that their benefits are additive when used in combination. We concluded that combination therapy with polysaccharide and MSCs is a promising clinical treatment for corneal alkali burns and may be applicable for other types of corneal disorder. PMID:25789487

  4. Direct Dating of Hominids Remains In Eurasia

    NASA Astrophysics Data System (ADS)

    Yokoyama, Y.; Falguères, C.

    When archaeological sites are associated with human remains, it is relevant to be able to date those valuable remains for different reasons. The main one is that it avoids the stratigraphical problems which can be due to intrusive burials in the sequence. The other reason consists in the fact that human bones may be encountered out of established stratigraphical context. On the other hand, the majority of dating methods currently used are destructive and can not be applied on these precious samples particularly when they are older than 40,000 years and can not be dated by radiocarbon. Since several years, we have developped a completely non-destructive method which consists in the measurement of human remains using the gamma -ray spectrometry. This technique has been used recently by other laboratories. We present here two important cases for the knowledge of human evolution in Eurasia. The first example is Qafzeh site in Israel where many human skeletons have been unearthed from burials associated with fauna and lithic artefacts. This site has been dated by several independent radiometric methods. So, it was possible to compare our gamma results with the other results yielded by the different methods. The second case concerns the most evolved Homo erectus found in Java, Indonesia, at Ngandong site, close to the Solo river. A recent debate has been focused on the age of these fossils and their direct dating is of outmost importance for the knowledge of settlement of Modern Humans in South-East Asia.

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

    NASA Astrophysics Data System (ADS)

    Balboni, Enrica; Burns, Peter C.

    2014-05-01

    The isotypical compounds (UO2)3(WO6)(H2O)5 (1), Ag(UO2)3(WO6)(OH)(H2O)3 (2), K(UO2)3(WO6)OH(H2O)4 (3), Rb(UO2)3(WO6)(OH)(H2O)3.5 (4), and Cs(UO2)3(WO6)OH(H2O)3 (5) were synthesized, characterized, and their structures determined. Each crystallizes in space group Cc. (1): a=12.979 (3), b=10.238 (2), c=11.302 (2), β=102.044 (2); (2): a=13.148 (2), b=9.520 (1), c=11.083 (2), β=101.568 (2); (3): a=13.111 (8), b=9.930 (6), c=11.242 (7), β=101.024 (7); (4): a=12.940 (2), b=10.231 (2), c=11.259(2), β=102.205 (2); (5): a=12.983 (3), b=10.191 (3), c=11.263 (4), β=101.661 (4). Compounds 1-5 are a framework of uranyl and tungsten polyhedra containing cation-cation interactions. The framework has three symmetrically distinct U(VI) cations, one tungsten, sixteen to eighteen oxygen atoms, and in 2-5, one monovalent cation. Each atom occupies a general position. Each U(VI) cation is present as a typical (UO2)2+ uranyl ion in an overall pentagonal bipyramidal coordination environment. Each pentagonal bipyramid shares two equatorial edges with two other pentagonal bipyramids, forming a trimer. Trimers are connected into chains by edge-sharing with WO6 octahedra. Chains are linked through cation-cation interactions between two symmetrically independent uranyl ions. This yields a remarkably complex system of intersecting channels that extend along [0 0 1] and [-1 1 0]. The cation exchange properties of 2 and 3 were characterized at room temperature and at 140 °C.

  6. Controlled in-situ dissolution of an alkali metal

    DOEpatents

    Jones, Jeffrey Donald; Dooley, Kirk John; Tolman, David Donald

    2012-09-11

    A method for the controllable dissolution of one or more alkali metals from a vessel containing a one or more alkali metals and/or one or more partially passivated alkali metals. The vessel preferably comprising a sodium, NaK or other alkali metal-cooled nuclear reactor that has been used. The alkali metal, preferably sodium, potassium or a combination thereof, in the vessel is exposed to a treatment liquid, preferably an acidic liquid, more preferably citric acid. Preferably, the treatment liquid is maintained in continuous motion relative to any surface of unreacted alkali metal with which the treatment liquid is in contact. The treatment liquid is preferably pumped into the vessel containing the one or more alkali metals and the resulting fluid is extracted and optionally further processed. Preferably, the resulting off-gases are processed by an off-gas treatment system and the resulting liquids are processed by a liquid disposal system. In one preferred embodiment, an inert gas is pumped into the vessel along with the treatment liquid.

  7. Ultrasonic coal washing to leach alkali elements from coals.

    PubMed

    Balakrishnan, S; Reddy, V Midhun; Nagarajan, R

    2015-11-01

    Deposition of fly ash particles onto heat-transfer surfaces is often one of the reasons for unscheduled shut-downs of coal-fired boilers. Fouling deposits encountered in convective sections of a boiler are characterized by arrival of ash particles in solidified (solid) state. Fouling is most frequently caused by condensation and chemical reaction of alkali vapors with the deposited ash particles creating a wet surface conducive to collect impacting ash particles. Hence, the amount of alkali elements present in coals, which, in turn, is available in the flue gas as condensable vapors, determines the formation and growth of fouling deposits. In this context, removal of alkali elements becomes vital when inferior coals having high-ash content are utilized for power generation. With the concept of reducing alkali elements present in a coal entering the combustor, whereby the fouling deposits can either be minimized or be weakened due to absence of alkali gluing effect, the ultrasonic leaching of alkali elements from coals is investigated in this study. Ultrasonic water-washing and chemical-washing, in comparison with agitation, are studied in order to estimate the intensification of the alkali removal process by sonication. PMID:26186840

  8. Alkali elemental and potassium isotopic compositions of Semarkona chondrules

    USGS Publications Warehouse

    Alexander, C.M. O'D.; Grossman, J.N.

    2005-01-01

    We report measurements of K isotope ratios in 28 Semarkona chondrules with a wide range of petrologic types and bulk compositions as well as the compositions of CPX-mesostasis pairs in 17 type I Semarkona chondrules, including two chondrules with radial alkali zonation and 19 type II chondrules. Despite the wide range in K/Al ratios, no systematic variations in K isotopic compositions were found. Semarkona chondrules do not record a simple history of Rayleigh-type loss of K. Experimentally determined evaporation rates suggest that considerable alkali evaporation would have occurred during chondrule formation. Nevertheless, based on Na CPX-mesostasis distribution coefficients, the alkali contents of the cores of most chondrules in Semarkona were probably established at the time of final crystallization. However, Na CPX-mesostasis distribution coefficients also show that alkali zonation in type I Semarkona chondrules was produced by entry of alkalis after solidification, probably during parent body alteration. This alkali metasomatism may have gone to completion in some chondrules. Our preferred explanation for the lack of systematic isotopic enrichments, even in alkali depleted type I chondrule cores, is that they exchanged with the ambient gas as they cooled. ?? The Meteoritical Society, 2005.

  9. Alkali ash material: a novel fly ash-based cement.

    PubMed

    Rostami, Hossein; Brendley, William

    2003-08-01

    The United States generates 110 million t of coal ash annually. Approximately 70 million t of this coal ash is fly ash, of which 27% is recycled and the remaining 73% is landfilled. Disposal of such a huge quantity of ash poses a significant environmental problem. A new cementitious material has been developed, called alkali ash material (AAM), which is used to produce concrete for construction. AAM can be used to create a variety of concrete strengths and could revolutionize the concrete product manufacturing industry due to its economic advantage. AAM contains 40-95% Class F fly ash and is used as cement to bind sand, stone, and fibers creating concrete. AAM concrete has been tested for strength, durability, mechanical properties, and, most importantly, economic viability. AAM concrete is economically and technically viable for many construction applications. Some properties include rapid strength gain (90% of ultimate in 1 d), high ultimate strengths (110 MPa or 16,000 psi in 1 d), excellent acid resistance, and freeze-thaw durability. AAM's resistance to chemical attack, such as sulfuric (H2SO4), nitric (HNO3), hydrochloric (HCl), and organic acids, is far better than portland cement concrete. AAM is resistant to freeze-thaw attack based on ASTM C-666 specifications. Potential immediate applications of AAM are blocks, pipe, median barriers, sound barriers, and overlaying materials. Eventual markets are high strength construction products, bridge beams, prestressed members, concrete tanks, highway appurtenances, and other concrete products. PMID:12966995

  10. Structural and Crystal Chemical Properties of Alkali Rare-earth Double Phosphates

    DOE PAGESBeta

    Farmer, James Matthew; Boatner, Lynn A.; Chakoumakos, Bryan C.; Rawn, Claudia J.; Richardson, Jim

    2016-01-01

    When appropriately activated, alkali rare-earth double phosphates of the form: M3RE(PO4)2 (where M denotes an alkali metal and RE represents either a rare-earth element or Y or Sc) are of interest for use as inorganic scintillators for radiation detection at relatively long optical emission wavelengths. These compounds exhibit layered crystal structures whose symmetry properties depend on the relative sizes of the rare-earth and alkali-metal cations. Single-crystal X-ray and powder neutron diffraction methods were used here to refine the structures of the series of rare-earth double phosphate compounds: K3RE(PO4)2 with RE = Lu, Er, Ho, Dy, Gd, Nd, Ce, plus Ymore » and Sc - as well as the compounds: A3Lu(PO4)2, with A = Rb, and Cs. The double phosphate K3Lu(PO4)2 was reported and structurally refined previously. This material had a hexagonal unit cell at room temperature with the Lu ion six-fold coordinated with oxygen atoms of the surrounding phosphate groups. Additionally two lower-temperature phases were observed for K3Lu(PO4)2. The first phase transition to a monoclinic P21/m phase occurred at ~230 K, and the Lu ion retained its six-fold coordination. The second K3Lu(PO4)2 phase transition occurred at ~130 K. The P21/m space group symmetry was retained, however, one of the phosphate groups rotated to increase the oxygen coordination number of Lu from six to seven. This structure then became isostructural with the room-temperature form of the compound K3Yb(PO4)2 reported here that also exhibits an additional high-temperature phase which occurs at T = 120 °C with a transformation to hexagonal P-3 space group symmetry and a Yb-ion coordination number reduction from seven to six. This latter result was confirmed using EXAFS. The single-crystal growth methods structural systematics, and thermal expansion properties of the present series of alkali rare-earth double phosphates, as determined by X-ray and neutron diffraction methods, are treated here.« less

  11. Structural and Crystal Chemical Properties of Alkali Rare-earth Double Phosphates

    SciTech Connect

    Farmer, James Matthew; Boatner, Lynn A.; Chakoumakos, Bryan C.; Rawn, Claudia J.; Richardson, Jim

    2016-01-01

    When appropriately activated, alkali rare-earth double phosphates of the form: M3RE(PO4)2 (where M denotes an alkali metal and RE represents either a rare-earth element or Y or Sc) are of interest for use as inorganic scintillators for radiation detection at relatively long optical emission wavelengths. These compounds exhibit layered crystal structures whose symmetry properties depend on the relative sizes of the rare-earth and alkali-metal cations. Single-crystal X-ray and powder neutron diffraction methods were used here to refine the structures of the series of rare-earth double phosphate compounds: K3RE(PO4)2 with RE = Lu, Er, Ho, Dy, Gd, Nd, Ce, plus Y and Sc - as well as the compounds: A3Lu(PO4)2, with A = Rb, and Cs. The double phosphate K3Lu(PO4)2 was reported and structurally refined previously. This material had a hexagonal unit cell at room temperature with the Lu ion six-fold coordinated with oxygen atoms of the surrounding phosphate groups. Additionally two lower-temperature phases were observed for K3Lu(PO4)2. The first phase transition to a monoclinic P21/m phase occurred at ~230 K, and the Lu ion retained its six-fold coordination. The second K3Lu(PO4)2 phase transition occurred at ~130 K. The P21/m space group symmetry was retained, however, one of the phosphate groups rotated to increase the oxygen coordination number of Lu from six to seven. This structure then became isostructural with the room-temperature form of the compound K3Yb(PO4)2 reported here that also exhibits an additional high-temperature phase which occurs at T = 120 °C with a transformation to hexagonal P-3 space group symmetry and a Yb-ion coordination number reduction from seven to six. This latter result was confirmed using EXAFS. The single

  12. Increasing Class C fly ash reduces alkali silica reactivity

    SciTech Connect

    Hicks, J.K.

    2007-07-01

    Contrary to earlier studies, it has been found that incremental additions of Class C fly ash do reduce alkali silica reactivity (ASR), in highly reactive, high alkali concrete mixes. AST can be further reduced by substituting 5% metakaolin or silica fume for the aggregate in concrete mixes with high (more than 30%) Class C fly ash substitution. The paper reports results of studies using Class C fly ash from the Labadie Station plant in Missouri which typically has between 1.3 and 1.45% available alkalis by ASTM C311. 7 figs.

  13. Why Do Some Cores Remain Starless?

    NASA Astrophysics Data System (ADS)

    Anathpindika, S.

    2016-08-01

    Prestellar cores, by definition, are gravitationally bound but starless pockets of dense gas. Physical conditions that could render a core starless (in the local Universe) is the subject of investigation in this work. To this end, we studied the evolution of four starless cores, B68, L694-2, L1517B, L1689, and L1521F, a VeLLO. We demonstrate: (i) cores contracted in quasistatic manner over a timescale on the order of ~ 105 yr. Those that remained starless briefly acquired a centrally concentrated density configuration that mimicked the profile of a unstable BonnorEbert sphere before rebounding, (ii) three cores viz. L694-2, L1689-SMM16, and L1521F remained starless despite becoming thermally super-critical. By contrast, B68 and L1517B remained sub-critical; L1521F collapsed to become a VeLLO only when gas-cooling was enhanced by increasing the size of dust-grains. This result is robust, for other starless cores viz. B68, L694-2, L1517B, and L1689 could also be similarly induced to collapse. The temperature-profile of starless cores and those that collapsed was found to be radically different. While in the former type, only very close to the centre of a core was there any evidence of decline in gas temperature, by contrast, a core of the latter type developed a more uniformly cold interior. Our principle conclusions are: (a) thermal super-criticality of a core is insufficient to ensure it will become protostellar, (b) potential star-forming cores (the VeLLO L1521F here), could be experiencing dust-coagulation that must enhance gasdust coupling and in turn lower gas temperature, thereby assisting collapse. This also suggests, mere gravitational/virial boundedness of a core is insufficient to ensure it will form stars.

  14. Structure-properties relations of aluminum trichloride- alkali thiocyanate ionic complex liquids

    NASA Astrophysics Data System (ADS)

    Liu, Changle

    1997-10-01

    In the pseudo binary systems, AlCl3-MSCN (where M = Li, Na, or K), low-melting solutions that are ionically- conducting and glass-forming occur over a wide composition range. The phase equilibria features are very similar to those of the analogous AlCl3-MCl binaries except for significantly lower liquidus temperatures, especially in more acidic compositions. The high conductivities of these liquids, which makes them of interest for rechargeable alkali battery systems, are attributed to a high degree of decoupling of cations from the complex anion matrix. A thorough Raman and FTIR characterization was made of the liquid structure. It appears that the anion complexes that make up the structure of AlCl3-MSCN liquids are formed by Lewis acid-base reactions very similar to those of the AlCl3-MCl binaries. Thus, in equimolar and acidic melts, the species Al(SCN)Cl3/sp- and Al2(SCN)Cl6/sp- are predominant. In contrast to the simpler AlCl3-MCl binaries, however, SCN-Cl ligand exchange reactions can also occur, forming complex anions with more than one SCN group. The low melting points, high cation conductivities, and the relative ease of supercooling and glass formation in the AlCl3- MSCN systems are believed to be related to the presence of these large and asymmetric complex anions.

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

    NASA Astrophysics Data System (ADS)

    Stux, Arnold M.

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

  16. Charge oscillations and structure for alkali-metal-doped polyacetylene

    NASA Astrophysics Data System (ADS)

    Baughman, R. H.; Murthy, N. S.; Eckhardt, H.; Kertesz, M.

    1992-11-01

    Symmetry-breaking structural and charge oscillations are calculated for (CpHp)- lattices (p=5 to 9) and used to predict Coulombic expansion coefficients, x-ray photoelectron spectra, and crystallographic features that can be compared with experimental results. Extension of these predictions to other dopant concentrations is provided by derived analytical expressions. The parameters for the infinite lattices are derived from oligomer-ion results obtained from modified neglect of differential overlap calculations. Such calculations on oligomer ions with different parametrizations provide essentially identical changes in charge and structural parameters upon doping and these changes are in excellent agreement with the results of infinite-chain calculations. The degree to which oligomer-ion segments retain the structural parameters of charged arrays for the infinite lattice is remarkable. Derived geometries and charge distributions indicate two different types of charged defects, solitons (or antisolitons) and split solitons (or split antisolitons), and the geometry and charge distribution of the latter defects is shown to correspond to the average of those for two soliton lattices that have a relative shift of two CH units. At least in the absence of an external Coulomb field, soliton and split-soliton lattices for p odd are quasidegenerate, and the lattices for p even consist of alternating sequences of solitons and split antisolitons. Large oscillations in local chain-axis direction are predicted, which is a consequence of both oscillations in bond angles and the nonequivalence of even (and odd) bond lengths. Including these effects provides predicted Coulombic expansion coefficients that are in good agreement with observations for Na-doped polyacetylene. Much smaller bond-angle oscillations are predicted for anion lattices than for cation lattices, which can be at least partially explained by Coulomb effects. Observed 13C NMR chemical shifts are consistent with

  17. The identification of submerged skeletonized remains.

    PubMed

    Byard, Roger W; Both, Katrin; Simpson, Ellie

    2008-03-01

    Examination was undertaken of skeletonized remains contained within 2 rubber boots dredged by a fishing boat from a depth of 145 m, approximately 185 km off the southern Australian coast in the Great Australian Bight. The boots had been manufactured in Australia in July 1993 and were of a type commonly used by local fishermen. Examination of the lower legs and feet revealed well-preserved bones with arthritic changes in keeping with an older male. DNA analyses using reference samples taken from relatives of fishermen who had disappeared in the area resulted in the identification of the victim as a 52-year-old prawn fisherman who had been swept off a boat over a decade earlier. DNA stability had been maintained by the low light, cold temperatures, and alkaline pH of the ocean floor. Integration of pathologic, anthropologic, and biologic analyses with police investigations enabled a positive identification to be made despite the unusual nature of the location of the remains and the time lapse since the disappearance of the victim. PMID:19749621

  18. Shotgun microbial profiling of fossil remains.

    PubMed

    Der Sarkissian, C; Ermini, L; Jónsson, H; Alekseev, A N; Crubezy, E; Shapiro, B; Orlando, L

    2014-04-01

    Millions to billions of DNA sequences can now be generated from ancient skeletal remains thanks to the massive throughput of next-generation sequencing platforms. Except in cases of exceptional endogenous DNA preservation, most of the sequences isolated from fossil material do not originate from the specimen of interest, but instead reflect environmental organisms that colonized the specimen after death. Here, we characterize the microbial diversity recovered from seven c. 200- to 13 000-year-old horse bones collected from northern Siberia. We use a robust, taxonomy-based assignment approach to identify the microorganisms present in ancient DNA extracts and quantify their relative abundance. Our results suggest that molecular preservation niches exist within ancient samples that can potentially be used to characterize the environments from which the remains are recovered. In addition, microbial community profiling of the seven specimens revealed site-specific environmental signatures. These microbial communities appear to comprise mainly organisms that colonized the fossils recently. Our approach significantly extends the amount of useful data that can be recovered from ancient specimens using a shotgun sequencing approach. In future, it may be possible to correlate, for example, the accumulation of postmortem DNA damage with the presence and/or abundance of particular microbes. PMID:24612293

  19. Decomposition Technique for Remaining Useful Life Prediction

    NASA Technical Reports Server (NTRS)

    Saha, Bhaskar (Inventor); Goebel, Kai F. (Inventor); Saxena, Abhinav (Inventor); Celaya, Jose R. (Inventor)

    2014-01-01

    The prognostic tool disclosed here decomposes the problem of estimating the remaining useful life (RUL) of a component or sub-system into two separate regression problems: the feature-to-damage mapping and the operational conditions-to-damage-rate mapping. These maps are initially generated in off-line mode. One or more regression algorithms are used to generate each of these maps from measurements (and features derived from these), operational conditions, and ground truth information. This decomposition technique allows for the explicit quantification and management of different sources of uncertainty present in the process. Next, the maps are used in an on-line mode where run-time data (sensor measurements and operational conditions) are used in conjunction with the maps generated in off-line mode to estimate both current damage state as well as future damage accumulation. Remaining life is computed by subtracting the instance when the extrapolated damage reaches the failure threshold from the instance when the prediction is made.

  20. So close: remaining challenges to eradicating polio.

    PubMed

    Toole, Michael J

    2016-01-01

    The Global Polio Eradication Initiative, launched in 1988, is close to achieving its goal. In 2015, reported cases of wild poliovirus were limited to just two countries - Afghanistan and Pakistan. Africa has been polio-free for more than 18 months. Remaining barriers to global eradication include insecurity in areas such as Northwest Pakistan and Eastern and Southern Afghanistan, where polio cases continue to be reported. Hostility to vaccination is either based on extreme ideologies, such as in Pakistan, vaccination fatigue by parents whose children have received more than 15 doses, and misunderstandings about the vaccine's safety and effectiveness such as in Ukraine. A further challenge is continued circulation of vaccine-derived poliovirus in populations with low immunity, with 28 cases reported in 2015 in countries as diverse as Madagascar, Ukraine, Laos, and Myanmar. This paper summarizes the current epidemiology of wild and vaccine-derived poliovirus, and describes the remaining challenges to eradication and innovative approaches being taken to overcome them. PMID:26971523

  1. 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

  2. Modulation of Framework and Centricity: Cation Size Effect in New Quaternary Selenites, ASc(SeO3)2 (A = Na, K, Rb, and Cs).

    PubMed

    Song, Seung Yoon; Ok, Kang Min

    2015-05-18

    Four new stoichiometrically equivalent quaternary scandium selenites, ASc(SeO3)2 (A = Na, K, Rb, and Cs) have been hydrothermally synthesized using A2CO3, Sc(NO3)3·xH2O (or ScO3), and SeO2 as starting materials. All four materials share similar bond networks that are composed of corner-shared distorted ScO6 octahedra and SeO3 trigonal pyramids. However, each material reveals different frameworks and centricities. Detailed structural analysis suggests that the structural variation is attributed to the difference in size and subsequent coordination number for the alkali metal cations. Powder second-harmonic generation (SHG) measurements on noncentrosymmetric (NCS) RbSc(SeO3)2 show that the compound has an SHG efficiency similar to that of (NH4)H2PO4. The observed SHG efficiency is due to the remaining net polarization after cancellation of oppositely aligned moments for SeO3 and ScO6 groups. Thorough characterizations such as spectroscopic, thermal, and elemental analyses for the new materials are presented as are dipole moment and out-of-center distortion calculations. PMID:25915517

  3. Tularemia vaccines: recent developments and remaining hurdles.

    PubMed

    Conlan, J Wayne

    2011-04-01

    Francisella tularensis subsp. tularensis is a facultative intracellular bacterial pathogen of humans and other mammals. Its inhaled infectious dose is very low and can result in very high mortality. Historically, subsp. tularensis was developed as a biological weapon and there are now concerns about its abuse as such by terrorists. A live attenuated vaccine developed pragmatically more than half a century ago from the less virulent holarctica subsp. is the sole prophylactic available, but it remains unlicensed. In recent years several other potential live, killed and subunit vaccine candidates have been developed and tested in mice for their efficacy against respiratory challenge with subsp. tularensis. This article will review these vaccine candidates and the development hurdles they face. PMID:21526941

  4. Some remaining problems in HCDA analysis. [LMFBR

    SciTech Connect

    Chang, Y.W.

    1981-01-01

    The safety assessment and licensing of liquid-metal fast breeder reactors (LMFBRs) requires an analysis on the capability of the reactor primary system to sustain the consequences of a hypothetical core-disruptive accident (HCDA). Although computational methods and computer programs developed for HCDA analyses can predict reasonably well the response of the primary containment system, and follow up the phenomena of HCDA from the start of excursion to the time of dynamic equilibrium in the system, there remain areas in the HCDA analysis that merit further analytical and experimental studies. These are the analysis of fluid impact on reactor cover, three-dimensional analysis, the treatment of the perforated plates, material properties under high strain rates and under high temperatures, the treatment of multifield flows, and the treatment of prestressed concrete reactor vessels. The purpose of this paper is to discuss the structural mechanics of HCDA analysis in these areas where improvements are needed.

  5. Electric field-induced softening of alkali silicate glasses

    NASA Astrophysics Data System (ADS)

    McLaren, C.; Heffner, W.; Tessarollo, R.; Raj, R.; Jain, H.

    2015-11-01

    Motivated by the advantages of two-electrode flash sintering over normal sintering, we have investigated the effect of an external electric field on the viscosity of glass. The results show remarkable electric field-induced softening (EFIS), as application of DC field significantly lowers the softening temperature of glass. To establish the origin of EFIS, the effect is compared for single vs. mixed-alkali silicate glasses with fixed mole percentage of the alkali ions such that the mobility of alkali ions is greatly reduced while the basic network structure does not change much. The sodium silicate and lithium-sodium mixed alkali silicate glasses were tested mechanically in situ under compression in external electric field ranging from 0 to 250 V/cm in specially designed equipment. A comparison of data for different compositions indicates a complex mechanical response, which is observed as field-induced viscous flow due to a combination of Joule heating, electrolysis and dielectric breakdown.

  6. The 4843 Alkali Metal Storage Facility Closure Plan

    SciTech Connect

    Not Available

    1991-06-01

    The 4843 AMSF has been used primarily to provide a centralized building to receive and store dangerous and mixed alkali metal waste, including sodium and lithium, which has been generated at the Fast Flux Test Facility and at various other Hanford Site operations that used alkali metals. Most of the dangerous and mixed alkali metal waste received consists of retired equipment from liquid sodium processes. The unit continues to store material. In general, only solid alkali metal waste that is water reactive is stored at the 4843 AMSF. The 4843 AMSF will be closed in a manner consistent with Ecology guidelines and regulations (WAC 173-303-610). The general closure procedure is detailed as follows.

  7. Hall Determination of Atomic Radii of Alkali Metals

    ERIC Educational Resources Information Center

    Houari, Ahmed

    2008-01-01

    I will propose here an alternative method for determining atomic radii of alkali metals based on the Hall measurements of their free electron densities and the knowledge of their crystal structure. (Contains 2 figures.)

  8. Method for intercalating alkali metal ions into carbon electrodes

    DOEpatents

    Doeff, M.M.; Ma, Y.; Visco, S.J.; DeJonghe, L.

    1995-08-22

    A low cost, relatively flexible, carbon electrode for use in a secondary battery is described. A method is provided for producing same, including intercalating alkali metal salts such as sodium and lithium into carbon.

  9. Method for intercalating alkali metal ions into carbon electrodes

    DOEpatents

    Doeff, Marca M.; Ma, Yanping; Visco, Steven J.; DeJonghe, Lutgard

    1995-01-01

    A low cost, relatively flexible, carbon electrode for use in a secondary battery is described. A method is provided for producing same, including intercalating alkali metal salts such as sodium and lithium into carbon.

  10. Electric field-induced softening of alkali silicate glasses

    SciTech Connect

    McLaren, C.; Heffner, W.; Jain, H.; Tessarollo, R.; Raj, R.

    2015-11-02

    Motivated by the advantages of two-electrode flash sintering over normal sintering, we have investigated the effect of an external electric field on the viscosity of glass. The results show remarkable electric field-induced softening (EFIS), as application of DC field significantly lowers the softening temperature of glass. To establish the origin of EFIS, the effect is compared for single vs. mixed-alkali silicate glasses with fixed mole percentage of the alkali ions such that the mobility of alkali ions is greatly reduced while the basic network structure does not change much. The sodium silicate and lithium-sodium mixed alkali silicate glasses were tested mechanically in situ under compression in external electric field ranging from 0 to 250 V/cm in specially designed equipment. A comparison of data for different compositions indicates a complex mechanical response, which is observed as field-induced viscous flow due to a combination of Joule heating, electrolysis and dielectric breakdown.

  11. Effect of cavitation on removal of alkali elements from coal

    NASA Astrophysics Data System (ADS)

    Srivalli, H.; Nirmal, L.; Nagarajan, R.

    2015-12-01

    The main impurities in coal are sulphur, ash and alkali. On combustion, the volatile forms of these impurities are either condensed on the boilers, or emitted in the form of potentially hazardous gases. The alkali elements present in coal help the fly ash particles adhere to boiler surfaces by providing a wet surface on which collection of these particles can take place. Use of ultrasonic techniques in cleaning of coal has stirred interest among researchers in recent times. Extraction of alkali elements by cavitation effect using low-frequency ultrasound, in the presence of reagents (HNO3 and H2O2) is reported in this paper. Powdered coal was dissolved with the reagent and exposed to ultrasonic fields of various frequencies at different time intervals. The treated solution is filtered and tested for alkali levels.

  12. 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.

  13. Preparation of poly(glycidylmethacrylate-divinylbenzene) weak acid cation exchange stationary phases with succinic anhydride, phthalic anhydride, and maleic anhydride for ion chromatography.

    PubMed

    Liu, Junwei; Wang, Yong; Wu, Shuchao; Zhang, Peimin; Zhu, Yan

    2016-08-01

    In this work, poly(glycidylmethacrylate-divinylbenzene) microspheres were prepared and applied for the preparation of weak acid cation exchange stationary phases. Succinic anhydride, phthalic anhydride, and maleic anhydride were selected as carboxylation reagents to prepare three weak acid cation exchangers by direct chemical derivatization reaction without solvent or catalyst. The diameters and dispersity of the microspheres were characterized by scanning electron microscopy; the amount of accessible epoxy groups and mechanical stability were also measured. The weak acid cation exchangers were characterized by Fourier transform infrared spectroscopy; the content of carboxyl groups was measured by traditional acid base titration method. The chromatographic properties were characterized and compared by separating alkali, alkaline earth metal ions and ammonium and polar amines. The separation properties enhanced in the order of succinic anhydride, phthalic anhydride, and maleic anhydride modified poly(glycidylmethacrylate-divinylbenzene) cation exchangers. PMID:27288092

  14. Rock Degradation by Alkali Metals: A Possible Lunar Erosion Mechanism.

    PubMed

    Naughton, J J; Barnes, I L; Hammond, D A

    1965-08-01

    When rocks melt under ultrahigh-vacuum conditions, their alkali components volatilize as metals. These metal vapors act to comminute polycrystalline rocks to their component minerals. The resultant powder is porous and loosely packed and its characteristics may be compatible with the lunar surface as revealed by the Ranger photographs. If meteorite impact or lunar volcanism has produced vaporization or areas of molten lava, alkali erosion may have given dust of this character in adjacent solid areas. PMID:17747570

  15. Electrochemical cell having an alkali-metal-nitrate electrode

    DOEpatents

    Roche, M.F.; Preto, S.K.

    1982-06-04

    A power-producing secondary electrochemical cell includes a molten alkali metal as the negative-electrode material and a molten-nitrate salt as the positive-electrode material. The molten material in the respective electrodes are separated by a solid barrier of alkali-metal-ion conducting material. A typical cell includes active materials of molten sodium separated from molten sodium nitrate and other nitrates in mixture by a layer of sodium ..beta..'' alumina.

  16. Gaseous protein cations are amphoteric

    SciTech Connect

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

    1997-02-19

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

  17. Alkali metal yttrium neo-pentoxide double alkoxide precursors to alkali metal yttrium oxide nanomaterials

    DOE PAGESBeta

    Boyle, Timothy J.; Neville, Michael L.; Sears, Jeremiah Matthew; Cramer, Roger

    2016-03-15

    In this study, a series of alkali metal yttrium neo-pentoxide ([AY(ONep)4]) compounds were developed as precursors to alkali yttrium oxide (AYO2) nanomaterials. The reaction of yttrium amide ([Y(NR2)3] where R=Si(CH3)3) with four equivalents of H-ONep followed by addition of [A(NR2)] (A=Li, Na, K) or Ao (Ao=Rb, Cs) led to the formation of a complex series of AnY(ONep)3+n species, crystallographically identified as [Y2Li3(μ3-ONep)(μ3-HONep)(μ-ONep)5(ONep)3(HONep)2] (1), [YNa2(μ3-ONep)4(ONep)]2 (2), {[Y2K3(μ3-ONep)3(μ-ONep)4(ONep)2(ηξ-tol)2][Y4K2(μ4-O)(μ3-ONep)8(ONep)4]•ηx-tol]} (3), [Y4K2(μ4-O)(μ3-ONep)8(ONep)4] (3a), [Y2Rb3(μ4-ONep)3(μ-ONep)6] (4), and [Y2Cs4(μ6-O)(μ3-ONep)6(μ3-HONep)2(ONep)2(ηx-tol)4]•tol (5). Compounds 1–5 were investigated as single source precursors to AYOx nanomaterials following solvothermal routes (pyridine, 185 °C for 24h). The final products after thermal processing weremore » found by powder X-ray diffraction experiments to be Y2O3 with variable sized particles based on transmission electron diffraction. Energy dispersive X-ray spectroscopy studies indicated that the heavier alkali metal species were present in the isolated nanomaterials.« less

  18. Alkali-slag cements for the immobilization of radioactive wastes

    SciTech Connect

    Shi, C.; Day, R.L.

    1996-12-31

    Alkali-slag cements consist of glassy slag and an alkaline activator and can show both higher early and later strengths than Type III Portland cement, if a proper alkaline activator is used. An examination of microstructure of hardened alkali-slag cement pastes with the help of XRD and SEM with EDAX shows that the main hydration product is C-S-H (B) with low C/S ratio and no crystalline substances exist such as Ca(OH){sub 2}, Al (OH){sub 3} and sulphoaluminates. Mercury intrusion tests indicate that hardened alkali-slag cement pastes have a lower porosity than ordinary Portland cement, and contain mainly gel pores. The fine pore structure of hardened alkali-slag cement pastes will restrict the ingress of deleterious substances and the leaching of harmful species such as radionuclides. The leachability of Cs{sup + } from hardened alkali-slag cement pastes is only half of that from hardened Portland cement. From all these aspects, it is concluded that alkali-slag cements are a better solidification matrix than Portland cement for radioactive wastes.

  19. Temperature dependence of elastic properties in alkali borate binary glasses

    NASA Astrophysics Data System (ADS)

    Kawashima, Mitsuru; Matsuda, Yu; Kojima, Seiji

    2011-05-01

    The elastic properties of alkali borate glasses, xM 2O·(100 - x)B 2O 3 (M = Li, Na, K, Rb, Cs, x = 14, 28), have been investigated by Brillouin scattering spectroscopy from room temperature up to 1100 °C. Above the glass transition temperature, Tg, the longitudinal sound velocity, VL, decreases markedly on heating. Such significant changes of the elastic properties result from the breakdown of the glass network above Tg. Alkali borate family with the same x shows the similar behavior in the temperature variations of VL up to around Tg. The absorption coefficient, αL, increases gradually above Tg. With the increase of the size of an alkali ion, the slope of VL just above Tg decreases. Since the fragility is related to the slope, the present results suggest that the fragility of alkali borate glasses increases as the size of alkali ion decreases. Such an alkali dependence of the fragility is discussed on the basis of the fluctuation of the boron coordination number.

  20. Two-phase alkali-metal experiments in reduced gravity

    SciTech Connect

    Antoniak, Z.I.

    1986-06-01

    Future space missions envision the use of large nuclear reactors utilizing either a single or a two-phase alkali-metal working fluid. The design and analysis of such reactors require state-of-the-art computer codes that can properly treat alkali-metal flow and heat transfer in a reduced-gravity environment. A literature search of relevant experiments in reduced gravity is reported on here, and reveals a paucity of data for such correlations. The few ongoing experiments in reduced gravity are noted. General plans are put forth for the reduced-gravity experiments which will have to be performed, at NASA facilities, with benign fluids. A similar situation exists regarding two-phase alkali-metal flow and heat transfer, even in normal gravity. Existing data are conflicting and indequate for the task of modeling a space reactor using a two-phase alkali-metal coolant. The major features of past experiments are described here. Data from the reduced-gravity experiments with innocuous fluids are to be combined with normal gravity data from the two-phase alkali-metal experiments. Analyses undertaken here give every expectation that the correlations developed from this data base will provide a valid representation of alkali-metal heat transfer and pressure drop in reduced gravity.

  1. Reduction of phosphorus and alkali levels in coking coals

    SciTech Connect

    Hoare, I.C.; Waugh, A.B.

    1995-12-31

    A number of coals, though exhibiting desirable coking properties, can have undesirable levels of alkalis and phosphorus. All the phosphorus in the coal will report to the coke, eventually to the iron and thence to the steel, with adverse effects on its metallurgical properties. Alkalis have damaging effects on the blast furnace operation and can be responsible for loss of heat, loss of production, efficiency loss and reduced furnace life. Buyers of coking coal commonly specify such parameters as phosphorus in coal and alkalis in ash, with penalties and rejection over certain limits. With the introduction of new direct reduction technologies such as COREX and HISMELT, and others such as PCI, it is anticipated that coal producers will have even tighter phosphorus and alkali specifications imposed on their products. Phosphorus is predominantly inorganic in origin occurring in a wide variety of minerals in coal, but its main source is apatite. It can be found mainly in the lower density fractions of the coal and intimately bound, so that conventional physical beneficiation techniques are relatively ineffective. CSIRO has developed a cost effective, selective chemical demineralization treatment, which can be applied to the problem of high alkali, high phosphorus coals. This particular technique makes use of unrefined organic acid, which also has the advantage of being low in cost and environmentally benign. In this paper, the effectiveness of acid demineralization of a number of coals is discussed, within the context of their phosphorus and alkali distributions throughout various size/density fractions.

  2. Small diatomic alkali molecules at ultracold temperatures

    NASA Astrophysics Data System (ADS)

    Wang, Tout Taotao

    This thesis describes experimental work done with two of the smallest diatomic alkali molecules, 6Li2 and 23Na 6Li, each formed out of its constituent atoms at ultracold temperatures. The 23Na6Li molecule was formed for the first time at ultracold temperatures, after previous attempts failed due to an incorrect assignment of Feshbach resonances in the 6Li+23Na system. The experiment represents successful molecule formation around the most difficult Feshbach resonance ever used, and opens up the possibility of transferring NaLi to its spin-triplet ground state, which has both magnetic and electric dipole moments and is expected to be long-lived. For 6Li2, the experimental efforts in this thesis have solved a long-standing puzzle of apparently long lifetimes of closed-channel fermion pairs around a narrow Feshbach resonance, finding that the lifetime is in fact short, as expected in the absence of Pauli suppression of collisions. Moreover, measurements of collisions of Li2 with free Li atoms demonstrates a striking first example of collisions involving molecules at ultracold temperatures described by physics beyond universal long-range van der Waals interactions.

  3. Superconductivity in alkali-doped fullerene nanowhiskers.

    PubMed

    Takeya, Hiroyuki; Konno, Toshio; Hirata, Chika; Wakahara, Takatsugu; Miyazawa, Kun'ichi; Yamaguchi, Takahide; Tanaka, Masashi; Takano, Yoshihiko

    2016-09-01

    Superconductivity in alkali metal-doped fullerene nanowhiskers (C60NWs) was observed in K3.3C60NWs, Rb3.0C60NWs and Cs2.0Rb1.0C60NWs with transition temperatures at 17, 25 and 26 K, respectively. Almost full shielding volume fraction (~80%) was observed in K3.3C60NWs when subjected to thermal treatment at 200 °C for a duration of 24 h. In contrast, the shielding fraction of Rb3.0C60NWs and Cs2.0Rb1.0C60NWs were calculated to be 8% and 6%, respectively. Here we report on an extensive investigation of the superconducting properties of these AC60NWs (A  =  K3.3, Rb3.0 and Cs2.0Rb1.0). These properties are compared to the ones reported on the corresponding conventional (single-crystal or powder) K-doped fullerene. We also evaluated the critical current densities of these C60NWs using the Bean model under an applied magnetic field up to 50 kOe. PMID:27385220

  4. The timing of alkali metasomatism in paleosols

    NASA Technical Reports Server (NTRS)

    MacFarlane, A. W.; Holland, H. D.

    1991-01-01

    We have measured the concentrations of rubidium and strontium and 87Sr/86Sr values of whole-rock samples from three paleosols of different ages. The oldest of the three weathering horizons, the 2,760 Ma Mt. Roe #1 paleosol in the Fortescue Group of Western Australia, experienced addition of Rb, and probably Sr, at 2,168 +/- 10 Ma. The intermediate paleosol, developed on the Hekpoort Basalt in South Africa, is estimated to have formed at 2,200 Ma, and yields a Rb-Sr isochron age of 1,925 +/- 32 Ma. The youngest of the three paleosols, developed on the Ongeluk basalt in Griqualand West, South Africa ca. 1,900 Ma, yielded a Rb-Sr age of 1,257 +/- 11 Ma. The Rb-Sr systematics of all three paleosols were reset during post-weathering metasomatism related to local or regional thermal disturbances. The Rb-Sr systematics of the paleosols were not subsequently disturbed. The near-complete removal of the alkali and alkaline earth elements from these paleosols during weathering made them particularly susceptible to resetting of their Rb-Sr systematics. Paleosols of this type are therefore sensitive indicators of the timing of thermal disturbances.

  5. Bioinorganic Chemistry of the Alkali Metal Ions.

    PubMed

    Kim, Youngsam; Nguyen, Thuy-Tien T; Churchill, David G

    2016-01-01

    The common Group 1 alkali metals are indeed ubiquitous on earth, in the oceans and in biological systems. In this introductory chapter, concepts involving aqueous chemistry and aspects of general coordination chemistry and oxygen atom donor chemistry are introduced. Also, there are nuclear isotopes of importance. A general discussion of Group 1 begins from the prevalence of the ions, and from a comparison of their ionic radii and ionization energies. While oxygen and water molecule binding have the most relevance to biology and in forming a detailed understanding between the elements, there is a wide range of basic chemistry that is potentially important, especially with respect to biological chelation and synthetic multi-dentate ligand design. The elements are widely distributed in life forms, in the terrestrial environment and in the oceans. The details about the workings in animal, as well as plant life are presented in this volume. Important biometallic aspects of human health and medicine are introduced as well. Seeing as the elements are widely present in biology, various particular endogenous molecules and enzymatic systems can be studied. Sodium and potassium are by far the most important and central elements for consideration. Aspects of lithium, rubidium, cesium and francium chemistry are also included; they help in making important comparisons related to the coordination chemistry of Na(+) and K(+). Physical methods are also introduced. PMID:26860297

  6. Superconductivity in alkali-doped fullerene nanowhiskers

    NASA Astrophysics Data System (ADS)

    Takeya, Hiroyuki; Konno, Toshio; Hirata, Chika; Wakahara, Takatsugu; Miyazawa, Kun’ichi; Yamaguchi, Takahide; Tanaka, Masashi; Takano, Yoshihiko

    2016-09-01

    Superconductivity in alkali metal-doped fullerene nanowhiskers (C60NWs) was observed in K3.3C60NWs, Rb3.0C60NWs and Cs2.0Rb1.0C60NWs with transition temperatures at 17, 25 and 26 K, respectively. Almost full shielding volume fraction (~80%) was observed in K3.3C60NWs when subjected to thermal treatment at 200 °C for a duration of 24 h. In contrast, the shielding fraction of Rb3.0C60NWs and Cs2.0Rb1.0C60NWs were calculated to be 8% and 6%, respectively. Here we report on an extensive investigation of the superconducting properties of these AC60NWs (A  =  K3.3, Rb3.0 and Cs2.0Rb1.0). These properties are compared to the ones reported on the corresponding conventional (single-crystal or powder) K-doped fullerene. We also evaluated the critical current densities of these C60NWs using the Bean model under an applied magnetic field up to 50 kOe.

  7. Body size prediction from juvenile skeletal remains.

    PubMed

    Ruff, Christopher

    2007-05-01

    There are currently no methods for predicting body mass from juvenile skeletal remains and only a very limited number for predicting stature. In this study, stature and body mass prediction equations are generated for each year from 1 to 17 years of age using a subset of the Denver Growth Study sample, followed longitudinally (n = 20 individuals, 340 observations). Radiographic measurements of femoral distal metaphyseal and head breadth are used to predict body mass and long bone lengths are used to predict stature. In addition, pelvic bi-iliac breadth and long bone lengths are used to predict body mass in older adolescents. Relative prediction errors are equal to or smaller than those associated with similar adult estimation formulae. Body proportions change continuously throughout growth, necessitating age-specific formulae. Adult formulae overestimate stature and body mass in younger juveniles, but work well in 17-year-olds from the sample, indicating that in terms of body proportions they are representative of the general population. To illustrate use of the techniques, they are applied to the juvenile Homo erectus (ergaster) KNM-WT 15000 skeleton. New body mass and stature estimates for this specimen are similar to previous estimates derived using other methods. Body mass estimates range from 50 to 53 kg, and stature was probably slightly under 157 cm, although a precise stature estimate is difficult to determine due to differences in linear body proportions between KNM-WT 15000 and the Denver reference sample. PMID:17295297

  8. Chandra Reveals Remains of Giant Eruption

    NASA Technical Reports Server (NTRS)

    2002-01-01

    This is a photo taken by NASA's Chandra X-ray Observatory that reveals the remains of an explosion in the form of two enormous arcs of multimillion-degree gas in the galaxy Centaurus A that appear to be part of a ring 25,000 light years in diameter. The size and location of the ring suggest that it could have been an explosion that occurred about 10 million years ago. A composite image made with radio (red and green), optical (yellow-orange), and X-ray data (blue) presents a sturning tableau of a turbulent galaxy. A broad band of dust and cold gas is bisected at an angle by opposing jets of high-energy particles blasting away from the supermassive black hole in the nucleus. Lying in a plane perpendicular to the jets are the two large arcs of x-ray emitting multi-million degree gas. This discovery can help astronomers better understand the cause and effect of violent outbursts from the vicinity of supermassive black holes of active galaxies. The Chandra program is managed by the Marshall Space Flight Center in Huntsville, Alabama.

  9. Relation between the electroforming voltage in alkali halide-polymer diodes and the bandgap of the alkali halide

    SciTech Connect

    Bory, Benjamin F.; Wang, Jingxin; Janssen, René A. J.; Meskers, Stefan C. J.; Gomes, Henrique L.; De Leeuw, Dago M.

    2014-12-08

    Electroforming of indium-tin-oxide/alkali halide/poly(spirofluorene)/Ba/Al diodes has been investigated by bias dependent reflectivity measurements. The threshold voltages for electrocoloration and electroforming are independent of layer thickness and correlate with the bandgap of the alkali halide. We argue that the origin is voltage induced defect formation. Frenkel defect pairs are formed by electron–hole recombination in the alkali halide. This self-accelerating process mitigates injection barriers. The dynamic junction formation is compared to that of a light emitting electrochemical cell. A critical defect density for electroforming is 10{sup 25}/m{sup 3}. The electroformed alkali halide layer can be considered as a highly doped semiconductor with metallic transport characteristics.

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

    PubMed

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

    2015-09-28

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

  11. Ghost Remains After Black Hole Eruption

    NASA Astrophysics Data System (ADS)

    2009-05-01

    NASA's Chandra X-ray Observatory has found a cosmic "ghost" lurking around a distant supermassive black hole. This is the first detection of such a high-energy apparition, and scientists think it is evidence of a huge eruption produced by the black hole. This discovery presents astronomers with a valuable opportunity to observe phenomena that occurred when the Universe was very young. The X-ray ghost, so-called because a diffuse X-ray source has remained after other radiation from the outburst has died away, is in the Chandra Deep Field-North, one of the deepest X-ray images ever taken. The source, a.k.a. HDF 130, is over 10 billion light years away and existed at a time 3 billion years after the Big Bang, when galaxies and black holes were forming at a high rate. "We'd seen this fuzzy object a few years ago, but didn't realize until now that we were seeing a ghost", said Andy Fabian of the Cambridge University in the United Kingdom. "It's not out there to haunt us, rather it's telling us something - in this case what was happening in this galaxy billions of year ago." Fabian and colleagues think the X-ray glow from HDF 130 is evidence for a powerful outburst from its central black hole in the form of jets of energetic particles traveling at almost the speed of light. When the eruption was ongoing, it produced prodigious amounts of radio and X-radiation, but after several million years, the radio signal faded from view as the electrons radiated away their energy. HDF 130 Chandra X-ray Image of HDF 130 However, less energetic electrons can still produce X-rays by interacting with the pervasive sea of photons remaining from the Big Bang - the cosmic background radiation. Collisions between these electrons and the background photons can impart enough energy to the photons to boost them into the X-ray energy band. This process produces an extended X-ray source that lasts for another 30 million years or so. "This ghost tells us about the black hole's eruption long after

  12. Ghost Remains After Black Hole Eruption

    NASA Astrophysics Data System (ADS)

    2009-05-01

    NASA's Chandra X-ray Observatory has found a cosmic "ghost" lurking around a distant supermassive black hole. This is the first detection of such a high-energy apparition, and scientists think it is evidence of a huge eruption produced by the black hole. This discovery presents astronomers with a valuable opportunity to observe phenomena that occurred when the Universe was very young. The X-ray ghost, so-called because a diffuse X-ray source has remained after other radiation from the outburst has died away, is in the Chandra Deep Field-North, one of the deepest X-ray images ever taken. The source, a.k.a. HDF 130, is over 10 billion light years away and existed at a time 3 billion years after the Big Bang, when galaxies and black holes were forming at a high rate. "We'd seen this fuzzy object a few years ago, but didn't realize until now that we were seeing a ghost", said Andy Fabian of the Cambridge University in the United Kingdom. "It's not out there to haunt us, rather it's telling us something - in this case what was happening in this galaxy billions of year ago." Fabian and colleagues think the X-ray glow from HDF 130 is evidence for a powerful outburst from its central black hole in the form of jets of energetic particles traveling at almost the speed of light. When the eruption was ongoing, it produced prodigious amounts of radio and X-radiation, but after several million years, the radio signal faded from view as the electrons radiated away their energy. HDF 130 Chandra X-ray Image of HDF 130 However, less energetic electrons can still produce X-rays by interacting with the pervasive sea of photons remaining from the Big Bang - the cosmic background radiation. Collisions between these electrons and the background photons can impart enough energy to the photons to boost them into the X-ray energy band. This process produces an extended X-ray source that lasts for another 30 million years or so. "This ghost tells us about the black hole's eruption long after

  13. Alkali-aggregate reactivity of typical siliceious glass and carbonate rocks in alkali-activated fly ash based geopolymers

    NASA Astrophysics Data System (ADS)

    Lu, Duyou; Liu, Yongdao; Zheng, Yanzeng; Xu, Zhongzi; Shen, Xiaodong

    2013-08-01

    For exploring the behaviour of alkali-aggregate reactivity (AAR) in alkali-activated geopolymeric materials and assessing the procedures for testing AAR in geopolymers, the expansion behaviour of fly ash based geopolymer mortars with pure silica glass and typical carbonate rocks were studied respectively by curing at various conditions, i.e. 23°C and 38°C with relative humidity over 95%, immersed in 1M NaOH solution at 80°C. Results show that, at various curing conditions, neither harmful ASR nor harmful ACR was observed in geopolymers with the criteria specified for OPC system. However, with the change of curing conditions, the geopolymer binder and reactive aggregates may experience different reaction processes leading to quite different dimensional changes, especially with additional alkalis and elevated temperatures. It suggests that high temperature with additional alkali for accelerating AAR in traditional OPC system may not appropriate for assessing the alkali-aggregate reactivity behaviour in geopolymers designed for normal conditions. On the other hand, it is hopeful to control the dimensional change of geopolymer mortar or concrete by selecting the type of aggregates and the appropriate curing conditions, thus changing the harmful AAR in OPC into beneficial AAR in geopolymers and other alkali-activated cementitious systems.

  14. On-chip fabrication of alkali-metal vapor cells utilizing an alkali-metal source tablet

    NASA Astrophysics Data System (ADS)

    Tsujimoto, K.; Ban, K.; Hirai, Y.; Sugano, K.; Tsuchiya, T.; Mizutani, N.; Tabata, O.

    2013-11-01

    We describe a novel on-chip microfabrication technique for the alkali-metal vapor cell of an optically pumped atomic magnetometer (OPAM), utilizing an alkali-metal source tablet (AMST). The newly proposed AMST is a millimeter-sized piece of porous alumina whose considerable surface area holds deposited alkali-metal chloride (KCl) and barium azide (BaN6), source materials that effectively produce alkali-metal vapor at less than 400 °C. Our experiments indicated that the most effective pore size of the AMST is between 60 and 170 µm. The thickness of an insulating glass spacer holding the AMST was designed to confine generated alkali metal to the interior of the vapor cell during its production, and an integrated silicon heater was designed to seal the device using a glass frit, melted at an optimum temperature range of 460-490 °C that was determined by finite element method thermal simulation. The proposed design and AMST were used to successfully fabricate a K cell that was then operated as an OPAM with a measured sensitivity of 50 pT. These results demonstrate that the proposed concept for on-chip microfabrication of alkali-metal vapor cells may lead to effective replacement of conventional glassworking approaches.

  15. Mixed alkali effect on the spectroscopic properties of alkali-alkaline earth oxide borate glasses

    NASA Astrophysics Data System (ADS)

    Srinivas, G.; Ramesh, B.; Shareefuddin, Md.; Chary, M. N.; Sayanna, R.

    2016-05-01

    The mixed alkali and alkaline earth oxide borate glass with the composition xK2O - (25-x) Li2O-12.5BaO-12.5MgO-50B2O3 (x = 0, 5, 10, 15, 20 and 25mol %) and doped with 1mol% CuO were prepared by the melt quenching technique. From the optical absorption spectra the optical band gap, electronic polarizability(α02-), interaction parameter (A), theoretical and experimental optical basicity (Λ) values were evaluated. From the Electron Paramagnetic Resonance (EPR) spectral data the number of spins (N) and susceptibility (χ) were evaluated. The values of (α02-), and (Λ) increases with increasing of K2O content and electronic polarizability and interaction parameter show opposite behaviuor which may be due to the creation of non-bridging oxygens and expansion of borate network. The reciprocal of susceptibility (1/χ) and spin concentration (N) as a function of K2O content, varied nonlinearly which may be due to creation of non-bridging oxygens in the present glass system. This may be attributed to mixed alkali effect (MAE).

  16. The reaction dynamics of alkali dimer molecules and electronically excited alkali atoms with simple molecules

    SciTech Connect

    Hou, H.

    1995-12-01

    This dissertation presents the results from the crossed molecular beam studies on the dynamics of bimolecular collisions in the gas phase. The primary subjects include the interactions of alkali dimer molecules with simple molecules, and the inelastic scattering of electronically excited alkali atoms with O2. The reaction of the sodium dimers with oxygen molecules is described in Chapter 2. Two reaction pathways were observed for this four-center molecule-molecule reaction, i.e. the formations of NaO2 + Na and NaO + NaO. NaO2 products exhibit a very anisotropic angular distribution, indicating a direct spectator stripping mechanism for this reaction channel. The NaO formation follows the bond breaking of O2, which is likely a result of a charge transfer from Na2 to the excited state orbital of O2-. The scattering of sodium dimers from ammonium and methanol produced novel molecules, NaNH3 and Na(CH3OH), respectively. These experimental observations, as well as the discussions on the reaction dynamics and the chemical bonding within these molecules, will be presented in Chapter 3. The lower limits for the bond dissociation energies of these molecules are also obtained. Finally, Chapter 4 describes the energy transfer between oxygen molecules and electronically excited sodium atoms.

  17. Structural implications of water dissolution in haplogranitic glasses from NMR spectroscopy: influence of total water content and mixed alkali effect

    NASA Astrophysics Data System (ADS)

    Schmidt, B. C.; Riemer, T.; Kohn, S. C.; Holtz, F.; Dupree, R.

    2001-09-01

    To study the effects of total water content and alkali substitution on the structure of aluminosilicate glasses, two series of glasses belonging to the ternary system Quartz (Qz)-Albite (Ab)-Orthoclase (Or) were synthesized and investigated with nuclear magnetic resonance (NMR) spectroscopy. Series I consisted of seven glasses with normative composition Ab 39Or 32Qz 29 (AOQ) and water contents ranging from 0 to 6 wt%. Series II consisted of dry and hydrous glasses (˜2.0 wt% H 2O) with five compositions along the join Qz 37Ab 63-Qz 34Or 66 (AQ-OQ) varying the alkali content (Na/K) at constant Si/Al ratio. All glasses were investigated with 1H, 23Na, 27Al and 29Si magic angle spinning (MAS) NMR. 29Si MAS spectra of AOQ glasses showed no change upon hydration, suggesting little variation of the Si environments although the large linewidth of the 29Si signal may hide the presence of some Si Q 3-OH. The isotropic chemical shift (δ iso) of 27Al showed no change upon hydration, regardless of the amount of dissolved water. The 27Al mean quadrupolar coupling constant (C q) decreased with increasing water content, indicating a general increase of symmetry of the charge distribution around Al, which suggests the absence of significant amounts of Al Q 3-OH. Nonetheless, the evolution of C q upon hydration suggests a correlation with OH concentration in the quenched glass. The evolution of 23Na isotropic chemical shifts upon hydration appears to be correlated with total water content or with the concentration of dissolved H 2O molecules. In general, the NMR data are consistent with the water solubility model of Kohn et al. (1989), involving the exchange of charge balancing cations by protons. However, in addition to the presence of molecular water, 1H-NMR results showed at least two types of OH groups of which one may be related to Al-OH. Although the small intensity of this signal indicates that only a minor fraction of OH groups is present in this species, it demonstrates

  18. Ciguatera: recent advances but the risk remains.

    PubMed

    Lehane, L; Lewis, R J

    2000-11-01

    Ciguatera is an important form of human poisoning caused by the consumption of seafood. The disease is characterised by gastrointestinal, neurological and cardiovascular disturbances. In cases of severe toxicity, paralysis, coma and death may occur. There is no immunity, and the toxins are cumulative. Symptoms may persist for months or years, or recur periodically. The epidemiology of ciguatera is complex and of central importance to the management and future use of marine resources. Ciguatera is an important medical entity in tropical and subtropical Pacific and Indian Ocean regions, and in the tropical Caribbean. As reef fish are increasingly exported to other areas, it has become a world health problem. The disease is under-reported and often misdiagnosed. Lipid-soluble, polyether toxins known as ciguatoxins accumulated in the muscles of certain subtropical and tropical marine finfish cause ciguatera. Ciguatoxins arise from biotransformation in the fish of less polar ciguatoxins (gambiertoxins) produced by Gambierdiscus toxicus, a marine dinoflagellate that lives on macroalgae, usually attached to dead coral. The toxins and their metabolites are concentrated in the food chain when carnivorous fish prey on smaller herbivorous fish. Humans are exposed at the end of the food chain. More than 400 species of fish can be vectors of ciguatoxins, but generally only a relatively small number of species are regularly incriminated in ciguatera. Ciguateric fish look, taste and smell normal, and detection of toxins in fish remains a problem. More than 20 precursor gambiertoxins and ciguatoxins have been identified in G. toxicus and in herbivorous and carnivorous fish. The toxins become more polar as they undergo oxidative metabolism and pass up the food chain. The main Pacific ciguatoxin (P-CTX-1) causes ciguatera at levels=0.1 microg/kg in the flesh of carnivorous fish. The main Caribbean ciguatoxin (C-CTX-1) is less polar and 10-fold less toxic than P-CTX-1. Ciguatoxins

  19. Probable Carbonate Fossilization Processes Within Dead Sea Microbial Remains

    NASA Technical Reports Server (NTRS)

    Morris, P. A.; Wentworth, S. J.; Thomas-Keprta, K. L.; Allen, C. C.; McKay, D. S.

    2001-01-01

    Microbial fossilization processes in the Dead Sea is primarily associated with the calcium cation. The putative fossilized microbes do not represent the reported living microbial population. Additional information is contained in the original extended abstract.

  20. Water Content of Lunar Alkali Fedlspar

    NASA Technical Reports Server (NTRS)

    Mills, R. D.; Simon, J. I.; Wang, J.; Alexander, C. M. O'D.; Hauri, E. H.

    2016-01-01

    Detection of indigenous hydrogen in a diversity of lunar materials, including volcanic glass, melt inclusions, apatite, and plagioclase suggests water may have played a role in the chemical differentiation of the Moon. Spectroscopic data from the Moon indicate a positive correlation between water and Th. Modeling of lunar magma ocean crystallization predicts a similar chemical differentiation with the highest levels of water in the K- and Th-rich melt residuum of the magma ocean (i.e. urKREEP). Until now, the only sample-based estimates of water content of KREEP-rich magmas come from measurements of OH, F, and Cl in lunar apatites, which suggest a water concentration of < 1 ppm in urKREEP. Using these data, predict that the bulk water content of the magma ocean would have <10 ppm. In contrast, estimate water contents of 320 ppm for the bulk Moon and 1.4 wt % for urKREEP from plagioclase in ferroan anorthosites. Results and interpretation: NanoSIMS data from granitic clasts from Apollo sample 15405,78 show that alkali feldspar, a common mineral in K-enriched rocks, can have approx. 20 ppm of water, which implies magmatic water contents of approx. 1 wt % in the high-silica magmas. This estimate is 2 to 3 orders of magnitude higher than that estimated from apatite in similar rocks. However, the Cl and F contents of apatite in chemically similar rocks suggest that these melts also had high Cl/F ratios, which leads to spuriously low water estimates from the apatite. We can only estimate the minimum water content of urKREEP (+ bulk Moon) from our alkali feldspar data because of the unknown amount of degassing that led to the formation of the granites. Assuming a reasonable 10 to 100 times enrichment of water from urKREEP into the granites produces an estimate of 100-1000 ppm of water for the urKREEP reservoir. Using the modeling of and the 100-1000 ppm of water in urKREEP suggests a minimum bulk silicate Moon water content between 2 and 20 ppm. However, hydrogen loss was

  1. Theory of Magnetotransport Anomalies in Alkali Metals

    NASA Astrophysics Data System (ADS)

    Zhu, Xiaodong

    The galvanomagnetic properties of alkali metals, especially those of potassium, are studied taking into account the existence of an incommensurate change-density wave (CDW) structure. Occurrence of the CDW broken symmetry truncates the Fermi surface with a large number of energy gaps. Furthermore, any macroscopic crystal is likely divided into CDW (')Q-domains. An orientational (')Q-texture leads to a preferred direction in the crystal. For such an exotic system the effective magnetoresistivity tensor is anomalous and is derived for various magnetic fields. The residual (zero-field) resistance is also anisotropic. For fields 0.5 - 3T, Hall coefficients are found to be anisotropic, and a longitudinal-transverse mixing effect is discovered. The diagonal elements of the magnetoresistivity tensor are found to have a linear magnetoresistance. When the field is increased above 4T sharp open-orbit magnetoresistance spectrum develops. From the theoretical magnetoresistivity tensor, the induced-torque amplitude and phase patterns for potassium spheres are calculated. The theory quantitatively explains all of the induced-torque anomalies found experimentally in the last fourteen years. An interacting electron system, which is free of the CDW instabilities, is also studied by considering its spin response to a weak sinusoidal magnetic field. The many-body correction G(,-)((')q,(omega)) caused by exchange and correlation is introduced to describe the correct wave -vector- and frequency-dependent spin susceptibility. The exact behavior of G(,-)((')q,(omega)) in the large-q limit is shown to be related to the pair distribution function g((')r) at r = 0. G(,-)((')q,(omega)) (--->) 4g(0)-1 /3, as q (--->) (INFIN).At metallic densities this value is negative, opposite in sign to the limit at small wave vectors. Thus the spin susceptibility for large wave vectors is suppressed, rather than enhanced, by many-body effects.

  2. Alkali content of alpine ultramafic rocks

    USGS Publications Warehouse

    Hamilton, W.; Mountjoy, W.

    1965-01-01

    The lower limit of abundance of sodium and potassium in ultramafic rocks is less than the threshold amount detectable by conventional analytical methods. By a dilutionaddition modification of the flame-spectrophotometric method, sodium and potassium have been determined in 40 specimens of alpine ultramafic rocks. Samples represent six regions in the United States and one in Australia, and include dunite, peridotite, pyroxenite, and their variably serpentinized and metamorphosed derivatives. The median value found for Na2O is 0.004 per cent, and the range of Na2O is 0.001-0.19. The median value for K2O is 0.0034 per cent and the range is 0.001-0.031 per cent. Alkali concentrations are below 0.01 per cent Na2O in 28 samples and below 0.01 per cent K2O in 35. Derivation of basalt magma from upper-mantle material similar to such ultramafic rocks, as has been postulated, is precluded by the relative amounts of sodium and potassium, which are from 200 to 600 times more abundant in basalt than in the ultramafic rocks. Similar factors apply to a number of other elements. No reasonable process could produce such concentrations in, for example, tens of thousands of cubic miles of uniform tholeiitic basalt. The ultramafic rocks might have originated either as magmatic crystal precipitates or as mantle residues left after fusion and removal of basaltic magma. Injection of ultramafic rocks to exposed positions is tectonic rather than magmatic. ?? 1965.

  3. Rice proteins, extracted by alkali and α-amylase, differently affect in vitro antioxidant activity.

    PubMed

    Wang, Zhengxuan; Liu, Ye; Li, Hui; Yang, Lin

    2016-09-01

    Alkali treatment and α-amylase degradation are different processes for rice protein (RP) isolation. The major aim of this study was to determine the influence of two different extraction methods on the antioxidant capacities of RPA, extracted by alkaline (0.2% NaOH), and RPE, extracted by α-amylase, during in vitro digestion for 2h with pepsin and for 3h with pancreatin. Upon pepsin-pancreatin digestion, the protein hydrolysates (RPA-S, RPE-S), which were the supernatants in the absence of undigested residue, and the whole protein digests (RPA, RPE), in which undigested residue remained, were measured. RPE exhibited the stronger antioxidant responses to free radical scavenging activity, metal chelating activity, and reducing power, whereas the weakest antioxidant capacities were produced by RPE-S. In contrast, no significant differences in antioxidant activity were observed between RPA and RPA-S. The present study demonstrated that the in vitro antioxidant responses induced by the hydrolysates and the protein digests of RPs could be affected differently by alkali treatment and α-amylase degradation, suggesting that the extraction is a vital processing step to modify the antioxidant capacities of RPs. The results of the current study indicated that the protein digests, in which undigested residues remained, could exhibit more efficacious antioxidant activity compared to the hydrolysates. PMID:27041309

  4. Cation coordination in oxychloride glasses

    NASA Astrophysics Data System (ADS)

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

    2003-02-01

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

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

    PubMed

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

    2015-04-24

    Na(+)/H(+) antiporters may recognize all alkali-metal cations as substrates but may transport them selectively. Plasma-membrane Zygosaccharomyces rouxii Sod2-22 antiporter exports Na(+) and Li(+), but not K(+). The molecular basis of this selectivity is unknown. We combined protein structure modeling, site-directed mutagenesis, phenotype analysis and cation efflux measurements to localize and characterize the cation selectivity region. A three-dimensional model of the ZrSod2-22 transmembrane domain was generated based on the X-ray structure of the Escherichia coli NhaA antiporter and primary sequence alignments with homologous yeast antiporters. The model suggested a close proximity of Thr141, Ala179 and Val375 from transmembrane segments 4, 5 and 11, respectively, forming a hydrophobic hole in the putative cation pathway's core. A series of mutagenesis experiments verified the model and showed that structural modifications of the hole resulted in altered cation selectivity and transport activity. The triple ZrSod2-22 mutant T141S-A179T-V375I gained K(+) transport capacity. The point mutation A179T restricted the antiporter substrate specificity to Li(+) and reduced its transport activity, while serine at this position preserved the native cation selectivity. The negative effect of the A179T mutation can be eliminated by introducing a second mutation, T141S or T141A, in the preceding transmembrane domain. Our experimental results confirm that the three residues found through modeling play a central role in the determination of cation selectivity and transport activity in Z. rouxii Na(+)/H(+) antiporter and that the cation selectivity can be modulated by repositioning a single local methyl group. PMID:25701798

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

    SciTech Connect

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

    1993-12-31

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

  7. The Production of Polycyclic Aromatic Hydrocarbon Anions in Inert Gas Matrices Doped with Alkali Metals. Electronic Absorption Spectra of the Pentacene Anion (C22H14(-))

    NASA Technical Reports Server (NTRS)

    Halasinski, Thomas M.; Hudgins, Douglas M.; Salama, Farid; Allamandola, Louis J.; Mead, Susan (Technical Monitor)

    1999-01-01

    The absorption spectra of pentacene (C22H14) and its radical cation (C22H14(+)) and anion (C22H14(-)) isolated in inert-gas matrices of Ne, Ar, and Kr are reported from the ultraviolet to the near-infrared. The associated vibronic band systems and their spectroscopic assignments are discussed together with the physical and chemical conditions governing ion (and counterion) production in the solid matrix. In particular, the formation of isolated pentacene anions is found to be optimized in matrices doped with alkali metal (Na and K).

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

    SciTech Connect

    Zho, Guangbin

    1992-12-31

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

  9. Nonbonded interactions in membrane active cyclic biopolymers. IV - Cation dependence

    NASA Technical Reports Server (NTRS)

    Radhakrishnan, R.; Srinivasan, S.; Prasad, C. V.; Brinda, S. R.; Macelroy, R. D.; Sundaram, K.

    1980-01-01

    Interactions of valinomycin and form of its analogs in several conformations with the central ions Li(+), Na(+), K(+), Rb(+) and Cs(+) are investigated as part of a study of the specific preference of valinomycin for potassium and the mechanisms of carrier-mediated ion transport across membranes. Ion binding energies and conformational potential energies are calculated taking into account polarization energy formulas and repulsive energy between the central ion and the ligand atoms for conformations representing various stages in ion capture and release for each of the two ring chiralities of valinomycin and its analogs. Results allow the prediction of the chirality and conformation most likely to be observed for a given analog, and may be used to synthesize analogs with a desired rigidity or flexibility. The binding energies with the alkali metal cations are found to decrease with increasing ion size, and to be smaller than the corresponding ion hydration energies. It is pointed out that the observed potassium preference may be explainable in terms of differences between binding and hydration energies. Binding energies are also noted to depend on ligand conformation.

  10. Iridium containing honeycomb Delafossites by topotactic cation exchange.

    PubMed

    Roudebush, John H; Ross, K A; Cava, R J

    2016-06-01

    We report the structure and magnetic properties of two new iridium-based honeycomb Delafossite compounds, Cu3NaIr2O6 and Cu3LiIr2O6, formed by a topotactic cation exchange reaction. The starting materials Na2IrO3 and Li2IrO3, which are based on layers of IrO6 octahedra in a honeycomb lattice separated by layers of alkali ions, are transformed to the title compounds by a topotactic exchange reaction through heating with CuCl below 450 °C; higher temperature reactions cause decomposition. The new compounds display dramatically different magnetic behavior from their parent compounds - Cu3NaIr2O6 has a ferromagnetic like magnetic transition at 10 K, while Cu3LiIr2O6 retains the antiferromagnetic transition temperature of its parent compound but displays significantly stronger dominance of antiferromagnetic coupling between spins. These results reveal that a surprising difference in the magnetic interactions between the magnetic Ir ions has been induced by a change in the non-magnetic interlayer species. A combination of neutron and X-ray powder diffraction is used for the structure refinement of Cu3NaIr2O6 and both compounds are compared to their parent materials. PMID:27147423

  11. Bone Marrow Mesenchymal Stem Cell Transplantation in a Rabbit Corneal Alkali Burn Model (A Histological and Immune Histo-chemical Study)

    PubMed Central

    Ahmed, Soheir Kamal; Soliman, Amel Ali; Omar, Sahar M. M.; Mohammed, Wafaa Rabee

    2015-01-01

    Background Alkali-burned corneas can seldom heal properly to restore corneal transparency. Treatment of this severe disorder of the ocular surface remains a challenge. Aim of the Work was to investigate whether systemically transplanted bone marrow mesenchymal stem cells (BM-MSCs) can promote corneal wound healing after alkali burn. Material and Methods Thirty five male New Zealand rabbits were used in this study. The animals were divided into three groups. Group I; the control group was sham operated. Group II; corneal alkali burn was created. Group III; underwent corneal alkali burn then treated with BM-MSCs. All corneas were collected after fourteen and twenty eight days. Evaluation using H&E, PAS & alkaline phosphatase reaction was carried out. Immune histo-chemical staining for CD44 and vimentin was performed as well. Results the corneal epithelium of (Group II) showed marked alterations. Vascularization, cellular infiltration and irregularity of the collagen fibers were also seen in the substantia propria. Increase in the thickness of the Descemet’s membrane was noticed as well. On the other hand, at the time of 28 days, Group III rabbits showed best histological results with nearly healed corneas compared to other groups. Meanwhile, vimentin was more strongly expressed in Group III assessing the differentiating ability of BM-MSCs. Conclusion BM-MSCs could effectively promote corneal alkali burn healing. PMID:26019756

  12. Optical properties and electronic structure of alkali doped SWNT

    NASA Astrophysics Data System (ADS)

    Nemes, Norbert M.; Fischer, John E.; Kamarás, Katalin; Borondics, Ferenc; Tanner, David B.; Rinzler, Andrew G.

    2003-03-01

    Alkali doped SWNT exhibit colors similar to alkali doped graphite (GIC). We study their electronic structure with IR reflectivity; the alkali dopants donate their valence electron to the SWNT host, so the free carrier concentration increases, shifting the Drude-edge into the visible spectral range. This is accompanied by a large shift of the Fermi-level, so the characteristic transitions between the 1D van Hove singularities of the undoped SWNT diminish. The presence of the alkali ions around the SWNT breaks the translational symmetry and increases coupling between parallel tubes within ropes. The momentum relaxation time shortens as the ropes become more three dimensional; alkali disorder contributes to the scattering. In p-type, HNO3 doped SWNT, the charge transfer is smaller; only the first subband of the semiconducting tubes gets depleted, shown by the disappearance of the first van Hove transition. This indicates a Fermi-level shift of ˜0.3 eV. The reflectivity has structure at low energy, which moves the Drude-peak to a sharp, intense peak at 0.1 eV in the optical conductivity, reminiscent of quasi-1D TTF-TCNQ.

  13. Multi-photon processes in alkali metal vapors

    NASA Astrophysics Data System (ADS)

    Gai, Baodong; Hu, Shu; Li, Hui; Shi, Zhe; Cai, Xianglong; Guo, Jingwei; Tan, Yannan; Liu, Wanfa; Jin, Yuqi; Sang, Fengting

    2015-02-01

    Achieving population inversion through multi-photon cascade pumping is almost always difficult, and most laser medium work under 1-photon excitation mechanism. But for alkali atoms such as cesium, relatively large absorption cross sections of several low, cascading energy levels enable them properties such as up conversion. Here we carried out research on two-photon excitation alkali fluorescence. Two photons of near infrared region are used to excite alkali atoms to n 2 D5/2, n 2 D3/2 or higher energy levels, then the blue fluorescence of (n+1) 2 P3/2,(n+1) 2 P1/2-->n 2 S1/2 are observed. Different pumping paths are tried and by the recorded spectra, transition routes of cesium are deducted and concluded. Finally the possibility of two-photon style DPALs (diode pumped alkali laser) are discussed, such alkali lasers can give output wavelengths in the shorter end of visual spectroscopy (400-460 nm) and are expected to get application in underwater communication and material laser processing.

  14. Alkali aluminosilicate melts and glasses: structuring at the middle range order of amorphous matter

    NASA Astrophysics Data System (ADS)

    Le Losq, C.; neuville, D. R.

    2012-12-01

    Rheological properties of silicate melts govern both magma ascension from the mantle to the surface of the earth and volcanological eruptions styles and behaviours. It is well known that several parameters impact strongly these properties, such as for instance the temperature, pressure, chemical composition and volatiles concentration, finally influencing eruptive behaviour of volcanoes. In this work, we will focus on the Na2O-K2O-Al2O3-SiO2 system, which is of a prime importance because it deals with a non-negligible part of natural melts, like for instance the Vesuvius (Italy) or Erebus (Antartica) magmas. In an oncoming paper in Chemical Geology (Le Losq and Neuville, 2012), we have communicated results of the study of mixing Na-K in tectosilicate melts containing a high concentration of silica (≥75mol%). In the present communication, we will enlarge this first point of view to tectosilicate melts presenting a lower silica concentration. We will first present our viscosity data, and then the Adam and Gibbs theory that allows theoretically modelling Na-K mixing in aluminosilicate melts by using the so-called "mixed alkali effect". On the basis of the rheological results, the Na-K mixing cannot be explained with the ideal "mixed alkali effect", which involves random exchange of Na-K cationic pairs. To go further and as rheological properties are directly linked with structural properties, we will present our first results obtained by Raman and NMR spectroscopy. These last ones provide important structural pieces of information on the polymerization state of glasses and melts, and also on the environment of tetrahedrally coordinated cations. Rheological and structural results all highlight that Na and K are not randomly distributed in aluminosilicate glasses and melts networks. Na melts present a network with some channels and a non-random distribution of Al and Si. K networks are different. They also present a non-random distribution of Al and Si, but in two sub

  15. Room temperature inorganic ``quasi-molten salts`` as alkali-metal electrolytes

    SciTech Connect

    Xu, K.; Zhang, S.; Angell, C.A.

    1996-11-01

    Room temperature inorganic liquids of high ionic conductivity have been prepared by reacting Lewis acid AlCl with sulfonyl chlorides. The mechanism is not clear at this time since a crystal structure study of the 1:1 complex with CH{sub 3}SO{sub 2}Cl (T{sub m} = 30 C) is not consistent with a simple chloride transfer to create AlClO{sub 4}{sup {minus}} anions. The liquid is in a state somewhere between ionic and molecular. A new term quasi-molten salt is adopted to describe this state. A comparably conducting liquid can be made using BCL{sub 3} in place of AlCl{sub 3}. Unlike their organic counterparts based on ammonium cations (e.g., pyridinium or imidazolium) which reduce in the presence of alkali metals, this inorganic class of cation shows great stability against electrochemical reduction (ca. {minus}1.0 V vs. Li{sup +}/Li), with the useful consequence that reversible lithium and sodium metal deposition/stripping can be supported. The electrochemical window for these quasi-salts with AlCl{sub 3} ranges up to 5.0 V, and their room temperature conductivities exceed 10{sup {minus}4} S/cm. They dissolve lithium and sodium tetrachloroaluminates up to mole fraction {approximately} 0.6 at 100 C and intermediate compositions are permanently stable at ambient. The resultant lithium or sodium salt solutions exhibit electrochemical windows of 4.5--5.0 V vs. Li{sup +}/Li or Na{sup +}/Na and show room temperature conductivities of 10{sup {minus}3.0}--10{sup {minus}2.5} S/cm. In preliminary charge/discharge tests, the cell Li/``quasi-ionic liquid electrolyte``/Li{sub 1+x}Mn{sub 2}O{sub 4} showed a discharge capacity of ca. 110 mAh/(g of cathode) and sustained 80% of the initial capacity after 60 cycles, indicating that these quasi-molten salt-based electrolytes are promising candidates for alkali-metal batteries.

  16. Maternal exposure to alkali, alkali earth, transition and other metals: Concentrations and predictors of exposure.

    PubMed

    Hinwood, A L; Stasinska, A; Callan, A C; Heyworth, J; Ramalingam, M; Boyce, M; McCafferty, P; Odland, J Ø

    2015-09-01

    Most studies of metals exposure focus on the heavy metals. There are many other metals (the transition, alkali and alkaline earth metals in particular) in common use in electronics, defense industries, emitted via combustion and which are naturally present in the environment, that have received limited attention in terms of human exposure. We analysed samples of whole blood (172), urine (173) and drinking water (172) for antimony, beryllium, bismuth, cesium, gallium, rubidium, silver, strontium, thallium, thorium and vanadium using ICPMS. In general most metals concentrations were low and below the analytical limit of detection with some high concentrations observed. Few factors examined in regression models were shown to influence biological metals concentrations and explained little of the variation. Further study is required to establish the source of metals exposures at the high end of the ranges of concentrations measured and the potential for any adverse health impacts in children. PMID:25984984

  17. Thermodynamics of Liquid Alkali Metals and Their Binary Alloys

    NASA Astrophysics Data System (ADS)

    Thakor, P. B.; Patel, Minal H.; Gajjar, P. N.; Jani, A. R.

    2009-07-01

    The theoretical investigation of thermodynamic properties like internal energy, entropy, Helmholtz free energy, heat of mixing (ΔE) and entropy of mixing (ΔS) of liquid alkali metals and their binary alloys are reported in the present paper. The effect of concentration on the thermodynamic properties of Ac1Bc2 alloy of the alkali-alkali elements is investigated and reported for the first time using our well established local pseudopotential. To investigate influence of exchange and correlation effects, we have used five different local field correction functions viz; Hartree(H), Taylor(T), Ichimaru and Utsumi(IU), Farid et al. (F) and Sarkar et al. (S). The increase of concentration C2, increases the internal energy and Helmholtz free energy of liquid alloy Ac1Bc2. The behavior of present computation is not showing any abnormality in the outcome and hence confirms the applicability of our model potential in explaining the thermodynamics of liquid binary alloys.

  18. Orbital Feshbach Resonance in Alkali-Earth Atoms.

    PubMed

    Zhang, Ren; Cheng, Yanting; Zhai, Hui; Zhang, Peng

    2015-09-25

    For a mixture of alkali-earth atomic gas in the long-lived excited state ^{3}P_{0} and the ground state ^{1}S_{0}, in addition to nuclear spin, another "orbital" index is introduced to distinguish these two internal states. In this Letter we propose a mechanism to induce Feshbach resonance between two atoms with different orbital and nuclear spin quantum numbers. Two essential ingredients are the interorbital spin-exchange process and orbital dependence of the Landé g factors. Here the orbital degrees of freedom plays a similar role as the electron spin degree of freedom in magnetic Feshbach resonance in alkali-metal atoms. This resonance is particularly accessible for the ^{173}Yb system. The BCS-BEC crossover in this system requires two fermion pairing order parameters, and displays a significant difference compared to that in an alkali-metal system. PMID:26451561

  19. Orbital Feshbach Resonance in Alkali-Earth Atoms

    NASA Astrophysics Data System (ADS)

    Zhang, Ren; Cheng, Yanting; Zhai, Hui; Zhang, Peng

    2015-09-01

    For a mixture of alkali-earth atomic gas in the long-lived excited state 3P0 and the ground state 1S0, in addition to nuclear spin, another "orbital" index is introduced to distinguish these two internal states. In this Letter we propose a mechanism to induce Feshbach resonance between two atoms with different orbital and nuclear spin quantum numbers. Two essential ingredients are the interorbital spin-exchange process and orbital dependence of the Landé g factors. Here the orbital degrees of freedom plays a similar role as the electron spin degree of freedom in magnetic Feshbach resonance in alkali-metal atoms. This resonance is particularly accessible for the 173Yb system. The BCS-BEC crossover in this system requires two fermion pairing order parameters, and displays a significant difference compared to that in an alkali-metal system.

  20. Release and sorption of alkali metals in coal conversion

    SciTech Connect

    Witthohn, A.; Oeltjen, L.; Hilpert, K.

    1998-07-01

    Released as gaseous species during coal combustion and gasification, alkali metal compounds cause high temperature corrosion especially at the gas turbine blading of coal-fired combined cycle power plants. Experimental and theoretical basic investigations are presented, which contribute to the understanding of the release and sorption of these contaminants. Knudsen effusion mass spectrometry was used to study the vaporization of coal ashes and slags at temperatures between 200 and 1,800 C and to determine the released alkali species and their partial pressures. The data base system FACT and the modified quasi-chemical model for non-ideal solutions were applied to model the thermodynamic behavior of coal slags and to determine material compositions of maximum alkali sorption capacity.

  1. Neuropsychiatric manifestations of alkali metal deficiency and excess.

    PubMed

    Yung, C Y

    1984-01-01

    The alkali metals from the Group IA of the periodic table (lithium, sodium, potassium, rubidium, cesium and francium) are reviewed. The neuropsychiatric aspects of alkali metal deficiencies and excesses (intoxications) are described. Emphasis was placed on lithium due to its clinical uses. The signs and symptoms of these conditions are characterized by features of an organic brain syndrome with delirium and encephalopathy prevailing. There are no clinically distinctive features that could be reliably used for diagnoses. Sodium and potassium are two essential alkali metals in man. Lithium is used as therapeutic agent in bipolar affective disorders. Rubidium has been investigated for its antidepressant effect in a group of psychiatric disorders. Cesium is under laboratory investigation for its role in carcinogenesis and in depressive illness. Very little is known of francium due to its great instability for experimental study. PMID:6395136

  2. Neuropsychiatric manifestations of alkali metal deficiency and excess

    SciTech Connect

    Yung, C.Y.

    1984-01-01

    The alkali metals from the Group IA of the periodic table (lithium, sodium, potassium, rubidium, cesium and francium) are reviewed. The neuropsychiatric aspects of alkali metal deficiencies and excesses (intoxications) are described. Emphasis was placed on lithium due to its clinical uses. The signs and symptoms of these conditions are characterized by features of an organic brain syndrome with delirium and encephalopathy prevailing. There are no clinically distinctive features that could be reliably used for diagnoses. Sodium and potassium are two essential alkali metals in man. Lithium is used as therapeutic agent in bipolar affective disorders. Rubidium has been investigated for its antidepressant effect in a group of psychiatric disorders. Cesium is under laboratory investigation for its role in carcinogenesis and in depressive illness. Very little is known of francium due to its great instability for experimental study.

  3. Theoretical study of the alkali and alkaline-earth monosulfides

    NASA Technical Reports Server (NTRS)

    Partridge, Harry; Langhoff, Stephen R.; Bauschlicher, Charles W., Jr.

    1988-01-01

    Ab initio calculations have been used to obtain accurate spectroscopic constants for the X2Pi and A2Sigma(+) states of the alkali sulfides and the X1Sigma(+), a3Pi, and A1Pi states of the alkaline-earth sulfides. In contrast to the alkali oxides, the alkali sulfides are found to have X2Pi ground states, due to the larger electrostatic interaction. Dissociation energies of 3.27 eV for BeS, 2.32 eV for MgS, 3.29 eV for CaS, and 3.41 eV for SrS have been obtained for the X1Sigma(+) states of the alkaline-earth sulfides, in good agreement with experimental results. Core correlation is shown to increase the Te values for the a3Pi and A1Pi states of MgS, CaS, and SrS.

  4. Superconductivity above 30 K in alkali-metal-doped hydrocarbon

    PubMed Central

    Xue, Mianqi; Cao, Tingbing; Wang, Duming; Wu, Yue; Yang, Huaixin; Dong, Xiaoli; He, Junbao; Li, Fengwang; Chen, G. F.

    2012-01-01

    The recent discovery of superconductivity with a transition temperature (Tc) at 18 K in Kxpicene has extended the possibility of high-Tc superconductors in organic materials. Previous experience based on similar hydrocarbons, like alkali-metal doped phenanthrene, suggested that even higher transition temperatures might be achieved in alkali-metals or alkali-earth-metals doped such polycyclic-aromatic-hydrocarbons (PAHs), a large family of molecules composed of fused benzene rings. Here we report the discovery of high-Tc superconductivity at 33 K in K-doped 1,2:8,9-dibenzopentacene (C30H18). To our best knowledge, it is higher than any Tc reported previously for an organic superconductor under ambient pressure. This finding provides an indication that superconductivity at much higher temperature may be possible in such PAHs system and is worthy of further exploration. PMID:22548129

  5. Alkali Activated Systems: Understanding the Influence of Curing Conditions and Activator Type/Chemistry on the Mechanical Strength and Chemical Structure of Fly Ash/Slag Systems

    NASA Astrophysics Data System (ADS)

    Chowdhury, Ussala

    The alkali activation of aluminosilicate materials as binder systems derived from industrial byproducts have been extensively studied due to the advantages they offer in terms enhanced material properties, while increasing sustainability by the reuse of industrial waste and byproducts and reducing the adverse impacts of OPC production. Fly ash and ground granulated blast furnace slag are commonly used for their content of soluble silica and aluminate species that can undergo dissolution, polymerization with the alkali, condensation on particle surfaces and solidification. The following topics are the focus of this thesis: (i) the use of microwave assisted thermal processing, in addition to heat-curing as a means of alkali activation and (ii) the relative effects of alkali cations (K or Na) in the activator (powder activators) on the mechanical properties and chemical structure of these systems. Unsuitable curing conditions instigate carbonation, which in turn lowers the pH of the system causing significant reductions in the rate of fly ash activation and mechanical strength development. This study explores the effects of sealing the samples during the curing process, which effectively traps the free water in the system, and allows for increased aluminosilicate activation. The use of microwave-curing in lieu of thermal-curing is also studied in order to reduce energy consumption and for its ability to provide fast volumetric heating. Potassium-based powder activators dry blended into the slag binder system is shown to be effective in obtaining very high compressive strengths under moist curing conditions (greater than 70 MPa), whereas sodium-based powder activation is much weaker (around 25 MPa). Compressive strength decreases when fly ash is introduced into the system. Isothermal calorimetry is used to evaluate the early hydration process, and to understand the reaction kinetics of the alkali powder activated systems. A qualitative evidence of the alkali

  6. Anti-inflammatory activity of cationic lipids.

    PubMed

    Filion, M C; Phillips, N C

    1997-10-01

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

  7. Selone-stabilized aryltellurenyl cations.

    PubMed

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

    2016-05-28

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

  8. Spill-Resistant Alkali-Metal-Vapor Dispenser

    NASA Technical Reports Server (NTRS)

    Klipstein, William

    2005-01-01

    A spill-resistant vessel has been developed for dispensing an alkali-metal vapor. Vapors of alkali metals (most commonly, cesium or rubidium, both of which melt at temperatures slightly above room temperature) are needed for atomic frequency standards, experiments in spectroscopy, and experiments in laser cooling. Although the present spill-resistant alkali-metal dispenser was originally intended for use in the low-gravity environment of outer space, it can also be used in normal Earth gravitation: indeed, its utility as a vapor source was confirmed by use of cesium in a ground apparatus. The vessel is made of copper. It consists of an assembly of cylinders and flanges, shown in the figure. The uppermost cylinder is a fill tube. Initially, the vessel is evacuated, the alkali metal charge is distilled into the bottom of the vessel, and then the fill tube is pinched closed to form a vacuum seal. The innermost cylinder serves as the outlet for the vapor, yet prevents spilling by protruding above the surface of the alkali metal, no matter which way or how far the vessel is tilted. In the event (unlikely in normal Earth gravitation) that any drops of molten alkali metal have been shaken loose by vibration and are floating freely, a mesh cap on top of the inner cylinder prevents the drops from drifting out with the vapor. Liquid containment of the equivalent of 1.2 grams of cesium was confirmed for all orientations with rubbing alcohol in one of the prototypes later used with cesium.

  9. Cohesive Energy-Lattice Constant and Bulk Modulus-Lattice Constant Relationships: Alkali Halides, Ag Halides, Tl Halides

    NASA Technical Reports Server (NTRS)

    Schlosser, Herbert

    1992-01-01

    In this note we present two expressions relating the cohesive energy, E(sub coh), and the zero pressure isothermal bulk modulus, B(sub 0), of the alkali halides. Ag halides and TI halides, with the nearest neighbor distances, d(sub nn). First, we show that the product E(sub coh)d(sub 0) within families of halide crystals with common crystal structure is to a good approximation constant, with maximum rms deviation of plus or minus 2%. Secondly, we demonstrate that within families of halide crystals with a common cation and common crystal structure the product B(sub 0)d(sup 3.5)(sub nn) is a good approximation constant, with maximum rms deviation of plus or minus 1.36%.

  10. Crown-Ether Derived Graphene Hybrid Composite for Membrane-Free Potentiometric Sensing of Alkali Metal Ions.

    PubMed

    Olsen, Gunnar; Ulstrup, Jens; Chi, Qijin

    2016-01-13

    We report the design and synthesis of newly functionalized graphene hybrid material that can be used for selective membrane-free potentiometric detection of alkali metal ions, represented by potassium ions. Reduced graphene oxide (RGO) functionalized covalently by 18-crown[6] ether with a dense surface coverage is achieved by the introduction of a flexible linking molecule. The resulting hybrid composite is highly stable and is capable of detecting potassium ions down to micromolar ranges with a selectivity over other cations (including Ca(2+), Li(+), Na(+), NH4(+)) at concentrations up to 25 mM. This material can be combined further with disposable chips, demonstrating its promise as an effective ion-selective sensing component for practical applications. PMID:26703780

  11. Interaction of alkali-metal overlayers with oxygen

    SciTech Connect

    Hrbek, J.; Xu, G.; Sham, T.K.; Shek, M.L.

    1989-05-01

    The interaction of oxygen with alkali metals (Li, Na, K, and Cs) was studied with valence and core-level photoemission (PE) using synchrotron radiation and by multiple mass thermal desorption (TDS). During a stepwise coadsorption of oxygen at 80 K, an increase in the emission intensity, a linewidth broadening, and a negative binding-energy shift of alkali-metal core levels is observed. Two stages of oxygen adsorption are identified in PE and TDS. In the low O/sub 2/ exposure range, an oxide species is formed; at higher exposures, peroxide and superoxide species are observed in Na, K, and Cs. The potassium--oxygen interaction is discussed in detail.

  12. Upgrading of petroleum oil feedstocks using alkali metals and hydrocarbons

    SciTech Connect

    Gordon, John Howard

    2014-09-09

    A method of upgrading an oil feedstock by removing heteroatoms and/or one or more heavy metals from the oil feedstock composition. This method reacts the oil feedstock with an alkali metal and an upgradant hydrocarbon. The alkali metal reacts with a portion of the heteroatoms and/or one or more heavy metals to form an inorganic phase separable from the organic oil feedstock material. The upgradant hydrocarbon bonds to the oil feedstock material and increases the number of carbon atoms in the product. This increase in the number of carbon atoms of the product increases the energy value of the resulting oil feedstock.

  13. Synergistic capture mechanisms for alkali and sulfur species from combustion

    SciTech Connect

    Peterson, T.W.; Shadman, F.; Wendt, J.O.L.; Wu, Baochun.

    1992-01-10

    Due to the generation of a wide variety of pollutants during coal combustion, research on the development of a multifunction sorbent for adsorbing SO{sub 2} and alkali compounds simultaneously is ongoing at the University of Arizona. The current work focuses on the thermodynamic behavior of the reacting system for alkali adsorption especially in gas phase. The temperature and pressure effects on sodium species and on the system are intensively investigated under the simulated flue gas composition condition. The interaction of sulfur dioxide with sodium chloride vapor and some other system elements is also explored.

  14. Feasibility of supersonic diode pumped alkali lasers: Model calculations

    SciTech Connect

    Barmashenko, B. D.; Rosenwaks, S.

    2013-04-08

    The feasibility of supersonic operation of diode pumped alkali lasers (DPALs) is studied for Cs and K atoms applying model calculations, based on a semi-analytical model previously used for studying static and subsonic flow DPALs. The operation of supersonic lasers is compared with that measured and modeled in subsonic lasers. The maximum power of supersonic Cs and K lasers is found to be higher than that of subsonic lasers with the same resonator and alkali density at the laser inlet by 25% and 70%, respectively. These results indicate that for scaling-up the power of DPALs, supersonic expansion should be considered.

  15. Cation-coupled bicarbonate transporters.

    PubMed

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

    2014-10-01

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

  16. Cation-Coupled Bicarbonate Transporters

    PubMed Central

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

    2016-01-01

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

  17. Use of Complementary Cation And Anion Heavy Atom-Atom Salt Derivatives to Solve the Structure of Cytochrome P450 46a1

    SciTech Connect

    White, M.A.; Mast, N.; Bjorkhem, I.; Johnson, E.F.; Stout, C.D.; Pikuleva, I.A.

    2009-05-26

    Human cytochrome P450 46A1 (CYP46A1) is one of the key enzymes in cholesterol homeostasis in the brain. The crystallization and heavy-atom structure solution of an active truncated CYP46A1 in complex with the high-affinity substrate analogue cholesterol-3-sulfate (CH-3S) is reported. The 2.6 {angstrom} structure of CYP46A1-CH-3S was solved using both anion and cation heavy-atom salts. In addition to the native anomalous signal from the haem iron, an NaI anion halide salt derivative and a complementary CsCl alkali-metal cation salt derivative were used. The general implications of the use of halide and alkali-metal quick soaks are discussed. The importance of using isoionic strength buffers, the titration of heavy-atom salts into different ionic species and the role of concentration are considered. It was observed that cation/anion-binding sites will occasionally overlap, which could negatively impact upon mixed RbBr soaks used for multiple anomalous scatterer MAD (MMAD). The use of complementary cation and anion heavy-atom salt derivatives is a convenient and powerful tool for MIR(AS) structure solution.

  18. Use of complementary cation and anion heavy-atom salt derivatives to solve the structure of cytochrome P450 46A1

    SciTech Connect

    White, Mark Andrew; Mast, Natalia; Bjorkhem, Ingemar; Johnson, Eric F.; Stout, C. David; Pikuleva, Irina A.

    2008-05-01

    Crystallization and analysis of the MIRAS heavy-atom structure solution of human cytochrome P450 46A1 using NaI and CsCl quick soaks. Human cytochrome P450 46A1 (CYP46A1) is one of the key enzymes in cholesterol homeostasis in the brain. The crystallization and heavy-atom structure solution of an active truncated CYP46A1 in complex with the high-affinity substrate analogue cholesterol-3-sulfate (CH-3S) is reported. The 2.6 Å structure of CYP46A1–CH-3S was solved using both anion and cation heavy-atom salts. In addition to the native anomalous signal from the haem iron, an NaI anion halide salt derivative and a complementary CsCl alkali-metal cation salt derivative were used. The general implications of the use of halide and alkali-metal quick soaks are discussed. The importance of using isoionic strength buffers, the titration of heavy-atom salts into different ionic species and the role of concentration are considered. It was observed that cation/anion-binding sites will occasionally overlap, which could negatively impact upon mixed RbBr soaks used for multiple anomalous scatterer MAD (MMAD). The use of complementary cation and anion heavy-atom salt derivatives is a convenient and powerful tool for MIR(AS) structure solution.

  19. Influence of alkaline earth metals on molecular structure of 3-nitrobenzoic acid in comparison with alkali metals effect

    NASA Astrophysics Data System (ADS)

    Samsonowicz, M.; Regulska, E.; Lewandowski, W.

    2011-11-01

    The influence of beryllium, magnesium, calcium, strontium and barium cations on the electronic system of 3-nitrobenzoic acid was studied in comparison with studied earlier alkali metal ions [1]. The vibrational FT-IR (in KBr and ATR techniques) and 1H and 13C NMR spectra were recorded for 3-nitrobenzoic acid and its salts. Characteristic shifts in IR and NMR spectra along 3-nitrobenzoates of divalent metal series Mg → Ba were compared with series of univalent metal Li → Cs salts. Good correlations between the wavenumbers of the vibrational bands in the IR spectra for 3-nitrobenzoates and ionic potential, electronegativity, inverse of atomic mass, atomic radius and ionization energy of metals were found for alkaline earth metals as well as for alkali metals. The density functional (DFT) hybrid method B3LYP with two basis sets: 6-311++G** and LANL2DZ were used to calculate optimized geometrical structures of studied compounds. The theoretical wavenumbers and intensities of IR spectra as well as chemical shifts in NMR spectra were obtained. Geometric aromaticity indices, atomic charges, dipole moments and energies were also calculated. The calculated parameters were compared to experimental characteristic of studied compounds.

  20. Molecular origin of high free energy barriers for alkali metal ion transfer through ionic liquid-graphene electrode interfaces.

    PubMed

    Ivaništšev, Vladislav; Méndez-Morales, Trinidad; Lynden-Bell, Ruth M; Cabeza, Oscar; Gallego, Luis J; Varela, Luis M; Fedorov, Maxim V

    2016-01-14

    In this work we study mechanisms of solvent-mediated ion interactions with charged surfaces in ionic liquids by molecular dynamics simulations, in an attempt to reveal the main trends that determine ion-electrode interactions in ionic liquids. We compare the interfacial behaviour of Li(+) and K(+) at a charged graphene sheet in a room temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate, and its mixtures with lithium and potassium tetrafluoroborate salts. Our results show that there are dense interfacial solvation structures in these electrolytes that lead to the formation of high free energy barriers for these alkali metal cations between the bulk and direct contact with the negatively charged surface. We show that the stronger solvation of Li(+) in the ionic liquid leads to the formation of significantly higher interfacial free energy barriers for Li(+) than for K(+). The high free energy barriers observed in our simulations can explain the generally high interfacial resistance in electrochemical storage devices that use ionic liquid-based electrolytes. Overcoming these barriers is the rate-limiting step in the interfacial transport of alkali metal ions and, hence, appears to be a major drawback for a generalised application of ionic liquids in electrochemistry. Some plausible strategies for future theoretical and experimental work for tuning them are suggested. PMID:26661060

  1. Ternary alkali-metal and transition metal or metalloid acetylides as alkali-metal intercalation electrodes for batteries

    DOEpatents

    Nemeth, Karoly; Srajer, George; Harkay, Katherine C; Terdik, Joseph Z

    2015-02-10

    Novel intercalation electrode materials including ternary acetylides of chemical formula: A.sub.nMC.sub.2 where A is alkali or alkaline-earth element; M is transition metal or metalloid element; C.sub.2 is reference to the acetylide ion; n is an integer that is 0, 1, 2, 3 or 4 when A is alkali element and 0, 1, or 2 when A is alkaline-earth element. The alkali elements are Lithium (Li), Sodium (Na), Potassium (K), Rubidium (Rb), Cesium (Cs) and Francium (Fr). The alkaline-earth elements are Berilium (Be), Magnesium (Mg), Calcium (Ca), Strontium (Sr), Barium (Ba), and Radium (Ra). M is a transition metal that is any element in groups 3 through 12 inclusive on the Periodic Table of Elements (elements 21 (Sc) to element 30 (Zn)). In another exemplary embodiment, M is a metalloid element.

  2. Water Adsorption on Free Cobalt Cluster Cations.

    PubMed

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

    2015-11-01

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

  3. Competitive interaction of monovalent cations with DNA from 3D-RISM.

    PubMed

    Giambaşu, George M; Gebala, Magdalena K; Panteva, Maria T; Luchko, Tyler; Case, David A; York, Darrin M

    2015-09-30

    The composition of the ion atmosphere surrounding nucleic acids affects their folding, condensation and binding to other molecules. It is thus of fundamental importance to gain predictive insight into the formation of the ion atmosphere and thermodynamic consequences when varying ionic conditions. An early step toward this goal is to benchmark computational models against quantitative experimental measurements. Herein, we test the ability of the three dimensional reference interaction site model (3D-RISM) to reproduce preferential interaction parameters determined from ion counting (IC) experiments for mixed alkali chlorides and dsDNA. Calculations agree well with experiment with slight deviations for salt concentrations >200 mM and capture the observed trend where the extent of cation accumulation around the DNA varies inversely with its ionic size. Ion distributions indicate that the smaller, more competitive cations accumulate to a greater extent near the phosphoryl groups, penetrating deeper into the grooves. In accord with experiment, calculated IC profiles do not vary with sequence, although the predicted ion distributions in the grooves are sequence and ion size dependent. Calculations on other nucleic acid conformations predict that the variation in linear charge density has a minor effect on the extent of cation competition. PMID:26304542

  4. Competitive interaction of monovalent cations with DNA from 3D-RISM

    PubMed Central

    Giambaşu, George M.; Gebala, Magdalena K.; Panteva, Maria T.; Luchko, Tyler; Case, David A.; York, Darrin M.

    2015-01-01

    The composition of the ion atmosphere surrounding nucleic acids affects their folding, condensation and binding to other molecules. It is thus of fundamental importance to gain predictive insight into the formation of the ion atmosphere and thermodynamic consequences when varying ionic conditions. An early step toward this goal is to benchmark computational models against quantitative experimental measurements. Herein, we test the ability of the three dimensional reference interaction site model (3D-RISM) to reproduce preferential interaction parameters determined from ion counting (IC) experiments for mixed alkali chlorides and dsDNA. Calculations agree well with experiment with slight deviations for salt concentrations >200 mM and capture the observed trend where the extent of cation accumulation around the DNA varies inversely with its ionic size. Ion distributions indicate that the smaller, more competitive cations accumulate to a greater extent near the phosphoryl groups, penetrating deeper into the grooves. In accord with experiment, calculated IC profiles do not vary with sequence, although the predicted ion distributions in the grooves are sequence and ion size dependent. Calculations on other nucleic acid conformations predict that the variation in linear charge density has a minor effect on the extent of cation competition. PMID:26304542

  5. Cation separations using a proton-ionizable macrocycle in a dual module hollow fiber membrane system

    SciTech Connect

    Izatt, R.M.; Lamb, J.D.; Bruening, R.L.; Chuan Wang; Edge, N.; Bradshaw, J.S.

    1993-01-01

    Separation of metal cations in aqueous solution using a proton-ionizable macrocycle in a dual module hollow fiber membrane system is described. The advantages of this system, such as easy access to all phases, rapid transport rates, and the potential for continuous operation are maintained with the proton-ionizable macrocycles which allow for proton driven transport. Transport is diffusion limited in the organic phase boundary layer near and on the fibers. Hence, the selectivity of the extraction system is maintained. Selective transport of Ag{sup +} over all other cations tested from neutral source phases and of K{sup +} over other alkali metal cations from basic source phases using a triazole-18-crown-6 carrier has been demonstrated. Selective K{sup +} transport from less basic source phases has been demonstrated using the more acidic thiopyridone-18-crown-6 ligand. However, the large aqueous partition of this ligand makes it difficult to maintain it in the organic phase. Design of the separation systems requires a knowledge of extraction equilibrium constants and partition coefficients. These data have been measured in order to understand these membrane systems.

  6. Cation Exchange in Dynamic 3D Porous Magnets: Improvement of the Physical Properties.

    PubMed

    Grancha, Thais; Acosta, Alvaro; Cano, Joan; Ferrando-Soria, Jesús; Seoane, Beatriz; Gascon, Jorge; Pasán, Jorge; Armentano, Donatella; Pardo, Emilio

    2015-11-16

    We report two novel three-dimensional porous coordination polymers (PCPs) of formulas Li4{Mn4[Cu2(Me3mpba)2]3}·68H2O (2) and K4{Mn4[Cu2(Me3mpba)2]3}·69H2O (3) obtained-via alkali cation exchange in a single-crystal to single-crystal process-from the earlier reported anionic manganese(II)-copper(II) PCP of formula Na4{Mn4[Cu2(Me3mpba)2]3}·60H2O (1) [Me3mpba(4-) = N,N'-2,4,6-trimethyl-1,3-phenylenebis(oxamate)]. This postsynthetic process succeeds where the direct synthesis in solution from the corresponding building blocks fails and affords significantly more robust PCPs with enhanced magnetic properties [long-range 3D magnetic ordering temperatures for the dehydrated phases (1'-3') of 2.0 (1'), 12.0 (2'), and 20.0 K (3')]. Changes in the adsorptive properties upon postsynthetic exchange suggest that the nature, electrostatic properties, mobility, and location of the cations within the framework are crucial for the enhanced structural stability. Overall, these results further confirm the potential of postsynthetic methods (including cation exchange) to obtain PCPs with novel or enhanced physical properties while maintaining unaltered their open-framework structures. PMID:26492551

  7. 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.

  8. A layered zinc oxalate possessing a 12-membered honeycomb aperture, stabilized by an amine and an alkali cation

    NASA Astrophysics Data System (ADS)

    Vaidhyanathan, R.; Natarajan, Srinivasan; Rao, C. N. R.

    2002-04-01

    A new layered anionic zinc oxalate of the formula, K[C 6N 2H 13][Zn 2(C 2O 4) 3].4H 2O containing 12-membered honeycomb apertures has been synthesized hydrothermally in the presence of DABCO and K +. A noteworthy feature of the structure is the presence of 12-membered apertures, aligned in such a way as to create pseudo one-dimensional tunnels as in zeolitic structures. The amine, K + and water molecules are present in the tunnels.

  9. 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.

  10. Investigation of anti-Relaxation coatings for alkali-metal vapor cells using surface science techniques

    SciTech Connect

    Seltzer, S. J.; Michalak, D. J.; Donaldson, M. H.; Balabas, M. V.; Barber, S. K.; Bernasek, S. L.; Bouchiat, M.-A.; Hexemer, A.; Hibberd, A. M.; Jackson Kimball, D. F.; Jaye, C.; Karaulanov, T.; Narducci, F. A.; Rangwala, S. A.; Robinson, H. G.; Shmakov, A. K.; Voronov, D. L.; Yashchuk, V. V.; Pines, A.; Budker, D.

    2010-10-11

    Many technologies based on cells containing alkali-metal atomic vapor benefit from the use of antirelaxation surface coatings in order to preserve atomic spin polarization. In particular, paraffin has been used for this purpose for several decades and has been demonstrated to allow an atom to experience up to 10?000 collisions with the walls of its container without depolarizing, but the details of its operation remain poorly understood. We apply modern surface and bulk techniques to the study of paraffin coatings in order to characterize the properties that enable the effective preservation of alkali spin polarization. These methods include Fourier transform infrared spectroscopy, differential scanning calorimetry, atomic force microscopy, near-edge x-ray absorption fine structure spectroscopy, and x-ray photoelectron spectroscopy. We also compare the light-induced atomic desorption yields of several different paraffin materials. Experimental results include the determination that crystallinity of the coating material is unnecessary, and the detection of C=C double bonds present within a particular class of effective paraffin coatings. Further study should lead to the development of more robust paraffin antirelaxation coatings, as well as the design and synthesis of new classes of coating materials.

  11. Responses of the murine esophageal microcirculation to acute exposure to alkali, acid, or hypochlorite

    PubMed Central

    Osman, M.; Russell, J.; Shukla, D.; Moghadamfalahi, M.; Granger, D.N.

    2008-01-01

    Background/Purpose Although ingestion of alkali- and/or hypochlorite-based household cleaners as well as strong acids remain a major cause of esophageal wall injury, little is known about the mechanisms that underlie the injury response to these toxic agents. This study examined the roles of vascular dysfunction and inflammation to the esophageal injury response to different caustic substances in mice. Methods The esophageal responses to NaOH (10%, 5% & 2.5%), KOH (10%, 5%, & 2.5%), NaOCl (5.25%), and HCl (10%, pH=2) were evaluated by intravital videomicroscopy, and histopathology. Intravital microscopy was used to monitor changes in the diameter of arterioles and venules, the adhesion and movement of leukocytes in venules, and time of cessation of arteriolar blood flow in mouse esophagus. The esophageal mucosa was exposed to caustic substances for 0–60 minutes prior to evaluation. Results The higher concentrations of NaOH and KOH elicited rapid stasis in both arterioles and venules, which was accompanied by arteriolar constriction and thrombosis. An accumulation of adherent leukocytes in venules was not observed with any agent. Histopathologic evaluation revealed marked cellular and interstitial edema in the mucosa with alkali, while HCl and NaOCl decreased the thickness epithelial layer. Conclusion These findings suggest that ischemia and thrombosis are dominant processes, while inflammation is less important, in the pathogenesis of acute corrosive injury to the esophageal mucosa. PMID:18779005

  12. Therapeutic Effects of Topical Netrin-4 Inhibits Corneal Neovascularization in Alkali-Burn Rats

    PubMed Central

    Han, Yun; Shao, Yi; Liu, Tingting; Qu, Yang-Luowa; Li, Wei; Liu, Zuguo

    2015-01-01

    Netrins are secreted molecules involved in axon guidance and angiogenesis. However, the role of netrins in the vasculature remains unclear. Netrin-4 and netrin-1 have been found to be either pro- or antiangiogenic factors. Previously, we found that netrin-1 acts as an anti-angiogenic factor in rats by inhibiting alkali burn-induced corneal neovascularization. Here, we further investigate the effects of netrin-4, another member of the same netrin family, on neovascularization in vitro and in vivo. We found that netrin-4 functions similarly as netrin-1 in angiogenesis. In vitro angiogenesis assay shows that netrin-4 affected human umbilical vein endothelial cell (HUVEC) tube formation, viability and proliferation, apoptosis, migration, and invasion in a dose-dependent manner. Netrin-4 was topically applied in vivo to alkali-burned rat corneas on day 0 (immediately after injury) and/or day 10 post-injury. Netrin-4 subsequently suppressed and reversed corneal neovascularization. Netrin-4 inhibited corneal epithelial and stromal cell apoptosis, inhibited vascular endothelial growth factor (VEGF), but promoted pigment epithelium-derived factor (PEDF) expression, decreased NK-KB p65 expression, and inhibits neutrophil and macrophage infiltration. These results indicate that netrin-4 shed new light on its potential roles in treatmenting for angiogenic diseases that affect the ocular surface, as well as other tissues. PMID:25853509

  13. Use of ancient copper slags in Portland cement and alkali activated cement matrices.

    PubMed

    Nazer, Amin; Payá, Jordi; Borrachero, María Victoria; Monzó, José

    2016-02-01

    Some Chilean copper slag dumps from the nineteenth century still remain, without a proposed use that encourages recycling and reduces environmental impact. In this paper, the copper slag abandoned in landfills is proposed as a new building material. The slags studied were taken from Playa Negra and Púquios dumps, both located in the region of Atacama in northern Chile. Pozzolanic activity in lime and Portland cement systems, as well as the alkali activation in pastes with copper slag cured at different temperatures, was studied. The reactivity of the slag was measured using thermogravimetric analysis (TGA), scanning electron microscopy (SEM), X-ray diffraction (XRD), electrical conductivity and pH in aqueous suspension and Fourier Transform Infrared Spectroscopy (FTIR). Furthermore, copper slag-Portland cement mortars with the substitution of 25% (by weight) of cement by copper slag and alkali-activated slag mortars cured at 20 and 65 °C were made, to determine the compressive strength. The results indicate that the ancient copper slags studied have interesting binding properties for the construction sector. PMID:26615227

  14. 40 CFR 721.5452 - Alkali metal salt of halogenated organoborate (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkali metal salt of halogenated... Specific Chemical Substances § 721.5452 Alkali metal salt of halogenated organoborate (generic). (a... generically as alkali metal salt of halogenated organoborate (PMN P-00-0638) is subject to reporting...

  15. 40 CFR 721.5985 - Fatty alkyl phosphate, alkali metal salt (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Fatty alkyl phosphate, alkali metal... Specific Chemical Substances § 721.5985 Fatty alkyl phosphate, alkali metal salt (generic). (a) Chemical... as a fatty alkyl phosphate, alkali metal salt (PMN P-99-0385) is subject to reporting under...

  16. 40 CFR 721.5452 - Alkali metal salt of halogenated organoborate (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkali metal salt of halogenated... Specific Chemical Substances § 721.5452 Alkali metal salt of halogenated organoborate (generic). (a... generically as alkali metal salt of halogenated organoborate (PMN P-00-0638) is subject to reporting...

  17. 40 CFR 721.5452 - Alkali metal salt of halogenated organoborate (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkali metal salt of halogenated... Specific Chemical Substances § 721.5452 Alkali metal salt of halogenated organoborate (generic). (a... generically as alkali metal salt of halogenated organoborate (PMN P-00-0638) is subject to reporting...

  18. 40 CFR 721.5452 - Alkali metal salt of halogenated organoborate (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkali metal salt of halogenated... Specific Chemical Substances § 721.5452 Alkali metal salt of halogenated organoborate (generic). (a... generically as alkali metal salt of halogenated organoborate (PMN P-00-0638) is subject to reporting...

  19. Origin of low sodium capacity in graphite and generally weak substrate binding of Na and Mg among alkali and alkaline earth metals

    NASA Astrophysics Data System (ADS)

    Liu, Yuanyue; Merinov, Boris V.; Goddard, William A., III

    2016-04-01

    It is well known that graphite has a low capacity for Na but a high capacity for other alkali metals. The growing interest in alternative cation batteries beyond Li makes it particularly important to elucidate the origin of this behavior, which is not well understood. In examining this question, we find a quite general phenomenon: among the alkali and alkaline earth metals, Na and Mg generally have the weakest chemical binding to a given substrate, compared with the other elements in the same column of the periodic table. We demonstrate this with quantum mechanics calculations for a wide range of substrate materials (not limited to C) covering a variety of structures and chemical compositions. The phenomenon arises from the competition between trends in the ionization energy and the ion-substrate coupling, down the columns of the periodic table. Consequently, the cathodic voltage for Na and Mg is expected to be lower than those for other metals in the same column. This generality provides a basis for analyzing the binding of alkali and alkaline earth metal atoms over a broad range of systems.

  20. Origin of low sodium capacity in graphite and generally weak substrate binding of Na and Mg among alkali and alkaline earth metals.

    PubMed

    Liu, Yuanyue; Merinov, Boris V; Goddard, William A

    2016-04-01

    It is well known that graphite has a low capacity for Na but a high capacity for other alkali metals. The growing interest in alternative cation batteries beyond Li makes it particularly important to elucidate the origin of this behavior, which is not well understood. In examining this question, we find a quite general phenomenon: among the alkali and alkaline earth metals, Na and Mg generally have the weakest chemical binding to a given substrate, compared with the other elements in the same column of the periodic table. We demonstrate this with quantum mechanics calculations for a wide range of substrate materials (not limited to C) covering a variety of structures and chemical compositions. The phenomenon arises from the competition between trends in the ionization energy and the ion-substrate coupling, down the columns of the periodic table. Consequently, the cathodic voltage for Na and Mg is expected to be lower than those for other metals in the same column. This generality provides a basis for analyzing the binding of alkali and alkaline earth metal atoms over a broad range of systems. PMID:27001855

  1. The magnetic moments of vanadium impurities in alkali hosts and induced spin current in alkali films

    NASA Astrophysics Data System (ADS)

    Song, Funing

    Thin quench-condensed films of Na, K, Rb, and Cs are covered with 1/100 of a monolayer of Vanadium. Then the V impurities are covered with several atomic layers of the host. The magnetization of the sandwiches is measured by means of the anomalous Hall effect. For V impurities on the surface of Na and K, a magnetic moment of 7 Bohr magnetons is observed. After coverage with the host, the V moment became 6.5muB for the Na host. These results contradict the favored atomic model (predicting 0.6muB) and the resonance model. The V moment on the surface and in the bulk of Rb and Cs is about 4muB and considerably smaller than the measured moments of V in Na. Furthermore, the sign of the anomalous Hall resistance changes from negative for the Na host to positive for the Cs host. This indicates a change of the electronic structure of the impurity (plus host environment) when going from Na to Cs hosts. Sandwiches of FeK and FeCs are prepared at helium temperature and under ultra-high vacuum. The mean free path within these sandwiches can exceed the film thickness by a factor of five. This implies almost perfect specular reflection of the electrons at the interfaces. Therefore, the mean free path of the film is strongly dependent on the degree of the specular reflection. Furthermore, the experiments suggest that the specular reflections for spin-up and spin-down electrons are different at the Fe interface, resulting in a spin current in the alkali films. In order to detect this current, dilute Pb impurities are condensed on top of the free surface of the alkali films. Strong spin-orbit scatterers, such as Pb, introduce an anomalous Hall effect in the presence of a spin current, which can be detected through straightforward Hall measurements. The results of the AHE experiments clearly indicate the existence of a local spin current.

  2. A new approach for preparation of magnetite-graphite composite: Intercalation of polyhydroxy iron cation into graphite oxide in L-arginine medium

    NASA Astrophysics Data System (ADS)

    Li, Shuqiong; Chen, Zhen; Jin, Yongdong; Chen, Shuihua; Wang, Hang; Geng, Junxia; Song, Qiang; Yang, Xiaodan; Ma, Lijian; Li, Shoujian; Qin, Zhi; Zheng, Chong

    2011-05-01

    A new approach to prepare magnetite nanoparticle pillared graphite has been put forward. The magnetic composite was normally obtained by calcining iron-intercalated graphite oxide, but the latter was prepared via intercalation reaction using polyhydroxy iron cation as iron precursor and pillaring agent, and a strong organic guanidine base, L-arginine, as alkaline agent and also intercalating agent. L-arginine, used herein instead of inorganic alkali, which would lead to the deoxygenation and reduction of graphite oxide into graphite, not only provided the alkaline condition for the formation of polyhydroxy iron cations, but also increased the interlayer spacing of graphite oxide to facilitate the intercalation of polyhydroxy iron cations into graphite oxide. The characterization by powder X-ray diffraction, transmission electron microscopy, vibrating sample magnetometer and nitrogen absorption indicated that the composite was nanoscale Fe 3O 4 pillared graphite with superparamagnetic property.

  3. Chlor-Alkali Industry: A Laboratory Scale Approach

    ERIC Educational Resources Information Center

    Sanchez-Sanchez, C. M.; Exposito, E.; Frias-Ferrer, A.; Gonzalez-Garaia, J.; Monthiel, V.; Aldaz, A.

    2004-01-01

    A laboratory experiment for students in the last year of degree program in chemical engineering, chemistry, or industrial chemistry is presented. It models the chlor-alkali process, one of the most important industrial applications of electrochemical technology and the second largest industrial consumer of electricity after aluminium industry.

  4. PVC waterproofing membranes and alkali-aggregated reaction in dams

    SciTech Connect

    Scuero, A.M.

    1995-12-31

    A waterproofing polyvinylchloride (PVC) based geocomposite was installed on two dams subject to alkali-aggregate reaction, to eliminate water intrusion and to protect the facing from further deterioration. The installation system allows drainage of the infiltrated water, thus accomplishing dehydration of the dam body. On one dam, the membrane also provided protection for future slot cutting.

  5. Influence of temperature on alkali stress adaptation in Listeria monocytogenes

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Listeria monocytogenes cells may induce alkali stress adaptation when exposed to sublethal concentrations of alkaline cleaners and sanitizers that may be frequently used in the food processing environment. In the present study, the effect of temperature on the induction and the stability of such alk...

  6. Assesment of Alkali Resistance of Basalt Used as Concrete Aggregates

    NASA Astrophysics Data System (ADS)

    al-Swaidani, Aref M.; Baddoura, Mohammad K.; Aliyan, Samira D.; Choeb, Walid

    2015-11-01

    The objective of this paper is to report a part of an ongoing research on the influence of using crushed basalt as aggregates on one of durability-related properties of concrete (i.e. alkali-silica reaction which is the most common form of Alkali-Aggregate Reaction). Alkali resistance has been assessed through several methods specified in the American Standards. Results of petrographic examination, chemical test (ASTM C289) and accelerated mortar bar test (ASTM C1260) have particularly been reported. In addition, the weight change and compressive strength of 28 days cured concrete containing basaltic aggregates were also reported after 90 days of exposure to 10% NaOH solution. Dolomite aggregate were used in the latter test for comparison. The experimental results revealed that basaltic rocks quarried from As-Swaida'a region were suitable for production of aggregates for concrete. According to the test results, the studied basalt aggregates can be classified as innocuous with regard to alkali-silica reaction. Further, the 10% sodium hydroxide attack did not affect the compressive strength of concrete.

  7. DUAL ALKALI TEST AND EVALUATION PROGRAM. VOLUME I. EXECUTIVE SUMMARY

    EPA Science Inventory

    Volume I of the report is an executive summary of the results of a three-task program to investigate, characterize, and evaluate the basic process chemistry and the various operating modes of sodium-based dual alkali scrubbing processes. The tasks were: I, laboratory studies at b...

  8. Structural models for alkali-metal complexes of polyacetylene

    NASA Astrophysics Data System (ADS)

    Murthy, N. S.; Shacklette, L. W.; Baughman, R. H.

    1990-02-01

    Structural models for a stage-2 complex are proposed for polyacetylene doped with less than about 0.1 potassium or rubidium atoms per carbon. These structures utilize as a basic motif an alkali-metal column surrounded by four planar-zig-zag polyacetylene chains, a structure found at the highest dopant levels. In the new stage-2 structures, each polyacetylene chain neighbors only one alkali-metal column, so the phase contains four polymer chains per alkali-metal column. Basic structural aspects for stage-1 and stage-2 structures are now established for both potassium- and rubidium-doped polyacetylene. X-ray-diffraction and electrochemical data show that undoped and doped phases coexist at low dopant concentrations (<0.06 K atom per C). X-ray-diffraction data, down to a Bragg spacing of 1.3 Å, for polyacetylene heavily doped with potassium (0.125-0.167 K atom per C) is fully consistent with our previously proposed stage-1 tetragonal unit cell containing two polyacetylene chains per alkali-metal column. There is no evidence for our samples requiring a distortion to a monoclinic unit cell as reported by others for heavily doped samples. The nature of structural transformations and the relationship between structure and electronic properties are discussed for potassium-doped polyacetylene.

  9. Modeling of alkali aggregate reaction effects in concrete dams

    SciTech Connect

    Capra, B.; Bournazel, J.P.; Bourdarot, E.

    1995-12-31

    Alkali Aggregate Reactions (AAR) are difficult to model due to the random distribution of the reactive sites and the imperfect knowledge of these chemical reactions. A new approach, using fracture mechanics and probabilities, capable to describe the anisotropic swelling of a structure is presented.

  10. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted halogenated pyridinol, alkali salt. 721.8900 Section 721.8900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances §...

  11. LABORATORY STUDY OF LIMESTONE REGENERATION IN DUAL ALKALI SYSTEMS

    EPA Science Inventory

    The report describes a series of open- and closed-loop laboratory bench scale experiments which were carried out to study parameters which affect the reaction of limestone with dual alkali flue gas desulfurization system process liquors. It gives details of several sets of operat...

  12. Method of assembling and sealing an alkali metal battery

    DOEpatents

    Elkins, P.E.; Bell, J.E.; Harlow, R.A.; Chase, G.G.

    1983-03-01

    A method of initially assembling and then subsequently hermetically sealing a container portion of an alkali metal battery to a ceramic portion of such a battery is disclosed. Sealing surfaces are formed respectively on a container portion and a ceramic portion of an alkali metal battery. These sealing surfaces are brought into juxtaposition and a material is interposed there between. This interposed material is one which will diffuse into sealing relationship with both the container portion and the ceramic portion of the alkali metal battery at operational temperatures of such a battery. A pressure is applied between these sealing surfaces to cause the interposed material to be brought into intimate physical contact with such juxtaposed surfaces. A temporary sealing material which will provide a seal against a flow of alkali metal battery reactants there through at room temperatures and is applied over the juxtaposed sealing surfaces and material interposed there between. The entire assembly is heated to an operational temperature so that the interposed material diffuses into the container portion and the ceramic portion to form a hermetic seal there between. The pressure applied to the juxtaposed sealing surfaces is maintained in order to ensure the continuation of the hermetic seal. 4 figs.

  13. Method of assembling and sealing an alkali metal battery

    DOEpatents

    Elkins, Perry E.; Bell, Jerry E.; Harlow, Richard A.; Chase, Gordon G.

    1983-01-01

    A method of initially assembling and then subsequently hermetically sealing a container portion of an alkali metal battery to a ceramic portion of such a battery is disclosed. Sealing surfaces are formed respectively on a container portion and a ceramic portion of an alkali metal battery. These sealing surfaces are brought into juxtaposition and a material is interposed therebetween. This interposed material is one which will diffuse into sealing relationship with both the container portion and the ceramic portion of the alkali metal battery at operational temperatures of such a battery. A pressure is applied between these sealing surfaces to cause the interposed material to be brought into intimate physical contact with such juxtaposed surfaces. A temporary sealing material which will provide a seal against a flow of alkali metal battery reactants therethrough at room temperatures and is applied over the juxtaposed sealing surfaces and material interposed therebetween. The entire assembly is heated to an operational temperature so that the interposed material diffuses into the container portion and the ceramic portion to form a hermetic seal therebetween. The pressure applied to the juxtaposed sealing surfaces is maintained in order to ensure the continuation of the hermetic seal.

  14. ALKALI-ACTIVATED SLAG CEMENTS AS A SUSTAINABLE BUILDING MATERIAL

    EPA Science Inventory

    The overall goal of this project is to develop and characterize alkali-activated slag cements with minimal carbon footprints, as well as to answer scientific questions that have yet to be satisfactorily addressed by prior research. These questions include the final disposition...

  15. Electro-optic contribution to Raman scattering from alkali halides

    SciTech Connect

    Mahan, G.D.; Subbaswamy, K.R.

    1986-06-15

    The electro-optic contributions to second-order Raman scattering and field-induced first-order scattering from alkali halides are calculated explicitly in terms of the ionic hyperpolarizability coefficients. The relevant local-field corrections are evaluated. Illustrative numerical results are presented.

  16. Aqueous alkali metal hydroxide insoluble cellulose ether membrane

    NASA Technical Reports Server (NTRS)

    Hoyt, H. E.; Pfluger, H. L. (Inventor)

    1969-01-01

    A membrane that is insoluble in an aqueous alkali metal hydroxide medium is described. The membrane is a resin which is a water-soluble C2-C4 hydroxyalkyl cellulose ether polymer and an insolubilizing agent for controlled water sorption, a dialytic and electrodialytic membrane. It is particularly useful as a separator between electrodes or plates in an alkaline storage battery.

  17. Stable Alkali-Metal Complexes of Hybrid Disila-Crown Ethers.

    PubMed

    Reuter, Kirsten; Buchner, Magnus R; Thiele, Günther; von Hänisch, Carsten

    2016-05-01

    The complexation ability of hybrid disilane and ethylene containing crown ether ring systems was analyzed using 1,2-disila[12]crown-4 (1), 1,2-disila[15]crown-5 (2), 1,2-disila[18]crown-6 (3), and 1,2,7,8-tetrasila[12]crown-4 (7). Alkali-metal complexes (Li(+), Na(+), K(+)) were obtained and analyzed via X-ray diffraction. The complex stability of [Li(1,2-disila[12]crown-4)](+) and [Li(1,2,7,8-tetrasila[12]crown-4)](+) was determined, in relation to the lithium complex of [12]crown-4, by density functional theory (DFT) calculations employing the BP86/def2-TZVP level of theory. In solution, the exchange of lithium cations between pure [12]crown-4 and hybrid [12]crown-4 is on even terms, as has been shown from the relative binding affinity of compounds 1 and 7 by means of dynamic proton nuclear magnetic resonance (NMR) spectroscopy. PMID:27082743

  18. UV laser-induced desorption mechanism analyzed through two-layer alkali halide samples.

    PubMed

    Fernández-Lima, F A; Ponciano, C R; da Silveira, E F

    2008-05-01

    Time of flight-mass spectrometry (TOF-MS) is used to analyze positive and negative desorbed ions generated by UV laser ablation of several alkali (X) halide (Y) salts. Most of the observed desorbed cluster ions have the structure (XY)(n)X(+) or (XY)(n)Y(-). Their desorption yields decrease as exp(-kn), where k approximately 2 for both series, suggesting that the neutral component (XY)(n) plays the dominant role in the desorption process. Mass spectrum measurements were performed for compound samples in which two salts (out of CsI, RbI, KBr, KCl and KI) are homogeneously mixed or disposed in two superposed layers. The detection of small new ion species and large cluster ions of the original salts supports the scenario that the uppermost layers are completely atomized while deep layers are emitted colder and fragmented: It is proposed that ns-pulsed laser induced desorption of ionic salts occurs via two sequential mechanisms: (1) ejection of cations and anions in the hot plume, followed by recombination into new cluster ions and (2) ejection of relatively cold preformed species originated from deep layers or from periphery of the irradiated region. PMID:18095386

  19. Rhizomes Help the Forage Grass Leymus chinensis to Adapt to the Salt and Alkali Stresses

    PubMed Central

    Li, Xiaoyu; Wang, Junfeng; Lin, Jixiang; Wang, Ying; Mu, Chunsheng

    2014-01-01

    Leymus chinensis has extensive ecological adaptability and can grow well in saline-alkaline soils. The knowledge about tolerance mechanisms of L. chinensis could be base for utilization of saline-alkaline soils and grassland restoration and rebuilding. Two neutral salts (NaCl : Na2SO4 = 9 : 1) and two alkaline salts (NaHCO3 : Na2CO3 = 9 : 1) with concentration of 0, 100, and 200 mmol/L were used to treat potted 35-day-old seedlings with rhizome growth, respectively. After 10 days, the biomass and number of daughter shoots all decreased, with more reduction in alkali than in salt stress. The rhizome biomass reduced more than other organs. The number of daughter shoots from rhizome was more than from tillers. Under both stresses, Na+ contents increased more in rhizome than in other organs; the reduction of K+ content was more in underground than aerial tissue. Anion ions or organic acids were absorbed to neutralize cations. Na+ content in stem and leaf increased markedly in high alkalinity (200 mmol/L), with accumulation of soluble sugar and organic acids sharply. Rhizomes help L. chinensis to adapt to saline and low alkaline stresses by transferring Na+. However, rhizomes lost the ability to prevent Na+ transport to aerial organs under high alkalinity, which led to severe growth inhibition of L. chinensis. PMID:25121110

  20. Rhizomes help the forage grass Leymus chinensis to adapt to the salt and alkali stresses.

    PubMed

    Li, Xiaoyu; Wang, Junfeng; Lin, Jixiang; Wang, Ying; Mu, Chunsheng

    2014-01-01

    Leymus chinensis has extensive ecological adaptability and can grow well in saline-alkaline soils. The knowledge about tolerance mechanisms of L. chinensis could be base for utilization of saline-alkaline soils and grassland restoration and rebuilding. Two neutral salts (NaCl : Na₂SO₄ = 9 : 1) and two alkaline salts (NaHCO₃ : Na₂CO₃ = 9 : 1) with concentration of 0, 100, and 200 mmol/L were used to treat potted 35-day-old seedlings with rhizome growth, respectively. After 10 days, the biomass and number of daughter shoots all decreased, with more reduction in alkali than in salt stress. The rhizome biomass reduced more than other organs. The number of daughter shoots from rhizome was more than from tillers. Under both stresses, Na(+) contents increased more in rhizome than in other organs; the reduction of K(+) content was more in underground than aerial tissue. Anion ions or organic acids were absorbed to neutralize cations. Na(+) content in stem and leaf increased markedly in high alkalinity (200 mmol/L), with accumulation of soluble sugar and organic acids sharply. Rhizomes help L. chinensis to adapt to saline and low alkaline stresses by transferring Na(+). However, rhizomes lost the ability to prevent Na(+) transport to aerial organs under high alkalinity, which led to severe growth inhibition of L. chinensis. PMID:25121110

  1. Design and Implementation of Alkali Activated Cement For Sustainable Development

    NASA Astrophysics Data System (ADS)

    Moseson, Alexander James

    Herein, progress is presented on the design and implementation of technology for sustainable development in general and international development in particular. Necessarily interdisciplinary, the work draws upon the tools and techniques of Mechanical, Materials, and Civil Engineering; and History & Politics. The work was conducted along two paths, the first being the theory and methodology of sustainable development. A flexible design and dissemination framework was developed, Technology Seeding, defined as: development by the transfer and participatory adaptation of appropriate proven conceptual designs. The methodology was developed in part through two case studies which implemented, respectively, wood-turning lathes in Tanzania and upland rice planters in Thailand. The second path is the design and investigation of alkali-activated cements (AACs) for practical use. Those developed herein, for US markets, comprise ground granulated blast furnace slag, soda ash (sodium carbonate), and up to 68 wt.% granular limestone. Mixture Design of Experiment (DOE) was utilized to guide empirical and theoretical analysis of performance (e.g. compressive strength), economic & ecological aspects (e.g. cost, CO2 production, energy consumption), and chemistry (e.g. Rietveld analysis of x-ray diffractograms). Models were derived to understand the impact of mix design on performance and for optimization. Successful formulations are hydraulic and cure at room temperature, with strengths as high as 41 MPa at 3 days and 65 MPa at 28 days. Some of these formulations, compared to OPC, are competitive in performance, reduce cost by up to 40%, and reduce both CO2 production and energy consumption by up to 97%. Major chemical products include calcium silicate hydrates / calcium aluminum silicate hydrates (C-(A)-S-H), gaylussite, and calcite (both newly formed and remaining from limestone). Calcite/dolomite and C-(A)-S-H both contribute to strength. A fraction of the limestone is consumed

  2. Alkali element constraints on Earth-Moon relations

    NASA Technical Reports Server (NTRS)

    Norman, M. D.; Drake, M. J.; Jones, J. H.

    1994-01-01

    Given their range of volatilities, alkali elements are potential tracers of temperature-dependent processes during planetary accretion and formation of the Earth-Moon system. Under the giant impact hypothesis, no direct connection between the composition of the Moon and the Earth is required, and proto-lunar material does not necessarily experience high temperatures. Models calling for multiple collisions with smaller planetesimals derive proto-lunar materials mainly from the Earth's mantle and explicitly invoke vaporization, shock melting and volatility-related fractionation. Na/K, K/Rb, and Rb/Cs should all increase in response to thermal volatization, so theories which derive the Moon substantially from Earth's mantle predict these ratios will be higher in the Moon than in the primitive mantle of the Earth. Despite the overall depletion of volatile elements in the Moon, its Na/K and K/Rb are equal to or less than those of Earth. A new model presented here for the composition of Earth's continental crust, a major repository of the alkali elements, suggests the Rb/Cs of the Moon is also less than that of Earth. Fractionation of the alkali elements between Earth and Moon are in the opposite sense to predictions based on the relative volatilities of these elements, if the Moon formed by high-T processing of Earth's mantle. Earth, rather than the Moon, appears to carry a signature of volatility-related fractionation in the alkali elements. This may reflect an early episode of intense heating on Earth with the Moon's alkali budget accreting from cooler material.

  3. 43 CFR 4730.2 - Disposal of remains.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... HORSES AND BURROS Destruction of Wild Horses or Burros and Disposal of Remains § 4730.2 Disposal of remains. Remains of wild horses or burros that die after capture shall be disposed of in accordance...

  4. 43 CFR 4730.2 - Disposal of remains.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... HORSES AND BURROS Destruction of Wild Horses or Burros and Disposal of Remains § 4730.2 Disposal of remains. Remains of wild horses or burros that die after capture shall be disposed of in accordance...

  5. 43 CFR 4730.2 - Disposal of remains.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... HORSES AND BURROS Destruction of Wild Horses or Burros and Disposal of Remains § 4730.2 Disposal of remains. Remains of wild horses or burros that die after capture shall be disposed of in accordance...

  6. 43 CFR 4730.2 - Disposal of remains.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... HORSES AND BURROS Destruction of Wild Horses or Burros and Disposal of Remains § 4730.2 Disposal of remains. Remains of wild horses or burros that die after capture shall be disposed of in accordance...

  7. 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.

  8. Interactions and low-energy collisions between an alkali ion and an alkali atom of a different nucleus

    NASA Astrophysics Data System (ADS)

    Rakshit, Arpita; Ghanmi, Chedli; Berriche, Hamid; Deb, Bimalendu

    2016-05-01

    We study theoretically interaction potentials and low-energy collisions between different alkali atoms and alkali ions. Specifically, we consider systems such as X + {{{Y}}}+, where X({{{Y}}}+) is either Li(Cs+) or Cs(Li+), Na(Cs+) or Cs(Na+) and Li(Rb+) or Rb(Li+). We calculate the molecular potentials of the ground and first two excited states of these three systems using a pseudopotential method and compare our results with those obtained by others. We derive ground-state scattering wave functions and analyze the cold collisional properties of these systems for a wide range of energies. We find that, in order to get convergent results for the total scattering cross sections for energies of the order 1 K, one needs to take into account at least 60 partial waves. The low-energy scattering properties calculated in this paper may serve as a precursor for experimental exploration of quantum collisions between an alkali atom and an alkali ion of a different nucleus.

  9. Chromium liquid waste inertization in an inorganic alkali activated matrix: leaching and NMR multinuclear approach.

    PubMed

    Ponzoni, Chiara; Lancellotti, Isabella; Barbieri, Luisa; Spinella, Alberto; Saladino, Maria Luisa; Martino, Delia Chillura; Caponetti, Eugenio; Armetta, Francesco; Leonelli, Cristina

    2015-04-01

    A class of inorganic binders, also known as geopolymers, can be obtained by alkali activation of aluminosilicate powders at room temperature. The process is affected by many parameters (curing time, curing temperature, relative humidity etc.) and leads to a resistant matrix usable for inertization of hazardous waste. In this study an industrial liquid waste containing a high amount of chromium (≈ 2.3 wt%) in the form of metalorganic salts is inertized into a metakaolin based geopolymer matrix. One of the innovative aspects is the exploitation of the water contained in the waste for the geopolymerization process. This avoided any drying treatment, a common step in the management of liquid hazardous waste. The evolution of the process--from the precursor dissolution to the final geopolymer matrix hardening--of different geopolymers containing a waste amount ranging from 3 to 20%wt and their capability to inertize chromium cations were studied by: i) the leaching tests, according to the EN 12,457 regulation, at different curing times (15, 28, 90 and 540 days) monitoring releases of chromium ions (Cr(III) and Cr(VI)) and the cations constituting the aluminosilicate matrix (Na, Si, Al); ii) the humidity variation for different curing times (15 and 540 days); iii) SEM characterization at different curing times (28 and 540 days); iv) the trend of the solution conductivity and pH during the leaching test; v) the characterization of the short-range ordering in terms of TOT bonds (where T is Al or Si) by (29)Si and (27)Al solid state magic-angle spinning nuclear magnetic resonance (ss MAS NMR) for geopolymers containing high amounts of waste (10-20%wt). The results show the formation of a stable matrix after only 15 days independently on the waste amount introduced; the longer curing times increase the matrices stabilities and their ability to immobilize chromium cations. The maximum amount of waste that can be inertized is around 10 wt% after a curing time of 28 days

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

    NASA Technical Reports Server (NTRS)

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

    1995-01-01

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

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

    SciTech Connect

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

    1994-12-31

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

  12. 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.

  13. 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

  14. [Effects of saline-alkali stress on electrical impedance spectroscopy parameters and ion contents in shoots of Ping'ou hybrid hazelnut].

    PubMed

    Zhang, Li; Jia, Zhi-Guo; Ma, Qing-Hua; Zhang, Gang; Wang, Gui-Xi

    2014-11-01

    To study the adaptability to salt-alkaline stress of Ping'ou hybrid hazelnut, 'Liaozhen 3' shoots which were treated with three types of stress neutral NaCl, alkaline Na2CO3, and mixed salt-alkali, and the changes in electrical impedance spectroscopy (EIS) parameters and mineral ion contents were subsequently determined. The correlations between the EIS parameters and mineral ion contents were analyzed. The results showed that with the increasing level of NaCl, specific high- frequency resistance (r), specific low-frequency resistance ( r(l)), specific intracellular resistance (r(i)) and specific extracellular resistance (r(e)) of shoots decreased firstly, then increased, and finally decreased again. However, these parameters increased gradually with the increasing level of Na2CO3, while r(l) and r(e) decreased slowly in the mixed salt-alkali treatments. The Na+ contents of shoots increased significantly under the three salt-alkali stresses with the order of NaCl stress > mixed salt-alkali stress > Na2CO3 stress. Furthermore, Na2CO3 stress resulted in the decreases in the contents of three elements Zn, B and Ca. The significant negative correlation was found between the sum of five cations and four EIS parameters r(l), r(e), relaxation time (τ) , and distribution coefficient of relaxation time (ψ). The shoots of 'Liaozhen 3' might be tolerant of Na2CO3 stress of 200 mmol · L(-1), while they could be resistant to NaCl stress of 100-150 mmol · L(-1). PMID:25898608

  15. [Measurement of Mole Ratio for Alkali Metal Mixture by Using Spectral Absorption Method].

    PubMed

    Zou, Sheng; Zhang, Hong; Chen, Yao; Chen, Xi-yuan

    2015-08-01

    The ratio of alkali metal mixture is one of the most important parameters in gauge head belonging to the ultra-sensitivity inertial measurement equipment, which is required to detect precisely. According to the feature that ratio of alkali metal is related to alkali metal vapor density, the theory of optical depth is used to detect the ratio of alkali metal in the present article. The result shows that the data got by the theory of optical depth compared with empirical formula differs at three orders of magnitude, which can't ensure the accuracy. By changing the data processing method, model between spectral absorption rate and temperature in cell is established. The temperature in alkali metal cell is calibrated by spectral absorption rate. The ratio of alkali metal atoms in the cell is analyzed by calculating the alkali density with empirical formula. The computational error is less than 10%. PMID:26672309

  16. Molecular simulation study on Hofmeister cations and the aqueous solubility of benzene.

    PubMed

    Ganguly, Pritam; Hajari, Timir; van der Vegt, Nico F A

    2014-05-22

    We study the ion-specific salting-out process of benzene in aqueous alkali chloride solutions using Kirkwood-Buff (KB) theory of solutions and molecular dynamics simulations with different empirical force field models for the ions and benzene. Despite inaccuracies in the force fields, the simulations indicate that the decrease of the Setchenow salting-out coefficient for the series NaCl > KCl > RbCl > CsCl is determined by direct benzene-cation correlations, with the larger cations showing weak interactions with benzene. Although ion-specific aqueous solubilities of benzene may be affected by indirect ion-ion, ion-water, and water-water correlations, too, these correlations are found to be unimportant, with little to no effect on the Setchenow salting-out coefficients of the various salts. We further considered LiCl, which is experimentally known to be a weaker salting-out agent than NaCl and KCl and, therefore, ranks at an unusual position within the Hofmeister cation series. The simulations indicate that hydrated Li(+) ions can take part of the benzene hydration shell while the other cations are repelled by it. This causes weaker Li(+) exclusion around the solute and a resulting, weaker salting-out propensity of LiCl compared to that of the other salts. Removing benzene-water and benzene-salt electrostatic interactions in the simulations does not affect this mechanism, which may therefore also explain the smaller effect of LiCl, as compared to that of NaCl or KCl, on aqueous solvation and hydrophobic interaction of nonpolar molecules. PMID:24792435

  17. Blue satellites of absorption spectrum study of sodium based excimer-pumped alkali vapor laser

    NASA Astrophysics Data System (ADS)

    Hu, Shu; Gai, Baodong; Guo, Jingwei; Tan, Yannan; Liu, Jinbo; Li, Hui; Cai, Xianglong; Shi, Zhe; Liu, Wanfa; Jin, Yuqi; Sang, Fengting

    2015-02-01

    Sodium based excimer-pump alkali laser (Na-XPAL) is expected to be an efficient method to generate sodium beacon light, but the information about the spectroscopic characters of Na-XPAL remains sparse so far. In this work, we utilized the relative fluorescence intensity to study the absorption spectrum of blue satellites of complexes of sodium with different collision partners. The yellow fluorescence of Na D1 and D2 line was clearly visible. After processing the fluorescence intensity and the input pumping laser relative intensity, we obtained the Na-CH4 system's blue satellites was from 553nm to 556nm. Meanwhile, we experimentally demonstrated the Na-Ar and Na-Xe system's wavelength range of blue satellites. Also, it was observed that the Na-Xe system's absorption was stronger than the other two systems.

  18. Sodium as Coupling Cation in Respiratory Energy Conversion.

    PubMed

    Fritz, Günter; Steuber, Julia

    2016-01-01

    Among the alkali cations, Na(+) has an extraordinary role in living cells since it is used to charge the battery of life. To this end, sophisticated protein complexes in biological membranes convert chemical energy obtained from oxidation of NADH, or hydrolysis of ATP, into an electrochemical gradient of sodium ions. Cells use this so-called sodium-motive force stored in energy-converting membranes for important processes like uptake of nutrients, motility, or expulsion of toxic compounds. The Na(+) pumps act in concert with other enzymes embedded in the lipid membrane, and together they form the respiratory chain which achieves the oxidation of NADH derived from nutrients under formation of an electrochemical sodium (or proton) gradient. We explain why Na(+) pumps are important model systems for the homologous, proton-translocating complexes, and hope to convince the reader that studying the Na(+)-translocating ATP synthase from the unimpressive bacterium Ilyobacter tartaricus had a big impact on our understanding of energy conversion by human ATP synthase. The Na(+)-translocating systems described here are either driven by the oxidation of NADH, the carrier of redox equivalents of cells, or by the hydrolysis of adenosine 5'-triphosphate, the universal high-energy compound of cells. The electrochemical energy provided by these respiratory Na(+) pumps, the NADH dehydrogenase or the ATPase, drives other Na(+) transport systems like the bacterial flagellum discussed in the last part of this chapter. The flagellar motor does not represent a Na(+) pump, but like ATPase, it operates by a rotational mechanism. By comparing these two Na(+) -translocating, rotary machines, we obtain new insight into the possible mechanisms of Na(+) transport through the stator proteins of the flagellar motor. Na(+) pumps are widespread in pathogenic bacteria where they play an important role in metabolism, making them novel targets for antibiotics. PMID:26860307

  19. Process for carbonaceous material conversion and recovery of alkali metal catalyst constituents held by ion exchange sites in conversion residue

    DOEpatents

    Sharp, David W.

    1980-01-01

    In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced, alkali metal constituents are recovered for the particles by contacting or washing them with an aqueous solution containing calcium or magnesium ions in an alkali metal recovery zone at a low temperature, preferably below about 249.degree. F. During the washing or leaching process, the calcium or magnesium ions displace alkali metal ions held by ion exchange sites in the particles thereby liberating the ions and producing an aqueous effluent containing alkali metal constituents. The aqueous effluent from the alkali metal recovery zone is then recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

  20. Cation locations and dislocations in zeolites

    NASA Astrophysics Data System (ADS)

    Smith, Luis James

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

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

    PubMed Central

    Knorr, Anne; Ludwig, Ralf

    2015-01-01

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

  2. 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.

  3. 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.

  4. Petrology and geochemistry of alkali gabbronorites from lunar breccia 67975

    NASA Technical Reports Server (NTRS)

    James, Odette B.; Flohr, Marta K.; Lindstrom, Marilyn M.

    1987-01-01

    Detailed results of petrologic and compositional studies of three clasts found in thin sections of the Apollo 16 lunar breccia 67975 and of four clasts extracted from the breccia (for instrumental neutron activation analysis) prior to thin sectioning are reported. The alkali gabbronorites of the breccia form two distinct subgroups, magnesian and ferroan. The magnesian gabbronorites are composed of bytownitic plagioclase, hypersthene, augite, a silica mineral, and trace Ba-rich K-feldspar. The ferroan gabbronorites are composed of ternary plagioclase, pigeonite, augite, Ba-rich K-feldspar, and a silica mineral. Trace minerals in both subgroups are apatite, REE-rich whitlockite, and zircon. The magnesian and ferroan alkali gabbronorites appear to have formed by progressive differentiation of the same, or closely related, parent REE-rich magmas.

  5. Alkali Halide Microstructured Optical Fiber for X-Ray Detection

    NASA Technical Reports Server (NTRS)

    DeHaven, S. L.; Wincheski, R. A.; Albin, S.

    2014-01-01

    Microstructured optical fibers containing alkali halide scintillation materials of CsI(Na), CsI(Tl), and NaI(Tl) are presented. The scintillation materials are grown inside the microstructured fibers using a modified Bridgman-Stockbarger technique. The x-ray photon counts of these fibers, with and without an aluminum film coating are compared to the output of a collimated CdTe solid state detector over an energy range from 10 to 40 keV. The photon count results show significant variations in the fiber output based on the materials. The alkali halide fiber output can exceed that of the CdTe detector, dependent upon photon counter efficiency and fiber configuration. The results and associated materials difference are discussed.

  6. Wetting Transitions of Inert Gases on Alkali Metal Surfaces

    NASA Astrophysics Data System (ADS)

    Bojan, M. J.; McDonald, I. A.; Cole, M. W.; Steele, W. A.

    1996-03-01

    Theoretical and experimental discoveries have been made recently of wetting and prewetting transitions of helium and hydrogen films on alkali metal surfaces [1,2]. New experiments show anomalous nonwetting behavior of Ne on Rb and Cs [3]. Building on earlier work [4], we have done and will describe results from the first Monte Carlo simulations showing wetting transitions for classical gases on alkali metal surfaces. * Research supported by an NSF Materials Research Group grant. 1. R. B.Hallock, J. Low Temp. Phys. 101, 31, 1995 2. M. W. Cole, J. Low Temp. Phys. 101, 25, 1995. 3. G. B. Hess, M. Sabatini, and M. H. W. Chan, unpublished 4. J. E. Finn and P. A. Monson, Phys. Rev. A 39, 6402, 1989.

  7. Alkali halide microstructured optical fiber for X-ray detection

    SciTech Connect

    DeHaven, S. L. E-mail: russel.a.wincheski@nasa.gov; Wincheski, R. A. E-mail: russel.a.wincheski@nasa.gov; Albin, S.

    2015-03-31

    Microstructured optical fibers containing alkali halide scintillation materials of CsI(Na), CsI(Tl), and NaI(Tl) are presented. The scintillation materials are grown inside the microstructured fibers using a modified Bridgman-Stockbarger technique. The x-ray photon counts of these fibers, with and without an aluminum film coating are compared to the output of a collimated CdTe solid state detector over an energy range from 10 to 40 keV. The photon count results show significant variations in the fiber output based on the materials. The alkali halide fiber output can exceed that of the CdTe detector, dependent upon photon counter efficiency and fiber configuration. The results and associated materials difference are discussed.

  8. Alkali elements in the Earth's core: Evidence from enstatite meteorites

    NASA Technical Reports Server (NTRS)

    Lodders, K.

    1995-01-01

    The abundances of alkali elements in the Earth's core are predicted by assuming that accretion of the Earth started from material similar in composition to enstatite chondrites and that enstatite achondrites (aubrites) provide a natural laboratory to study core-mantle differentiation under extremely reducing conditions. If core formation on the aubrite parent body is comparable with core formation on the early Earth, it is found that 2600 (+/- 1000) ppm Na, 550 (+/- 260) ppm K, 3.4 (+/- 2.1) ppm Rb, and 0.31 (+/- 0.24) ppm Cs can reside in the Earth's core. The alkali-element abundances are consistent with those predicted by independent estimates based on nebula condensation calculations and heat flow data.

  9. Coherent coupling of alkali atoms by random collisions.

    PubMed

    Katz, Or; Peleg, Or; Firstenberg, Ofer

    2015-09-11

    Random spin-exchange collisions in warm alkali vapor cause rapid decoherence and act to equilibrate the spin state of the atoms in the vapor. In contrast, here we demonstrate experimentally and theoretically a coherent coupling of one alkali species to another species, mediated by these random collisions. We show that the minor species (potassium) inherits the magnetic properties of the dominant species (rubidium), including its lifetime (T_{1}), coherence time (T_{2}), gyromagnetic ratio, and spin-exchange relaxation-free magnetic-field threshold. We further show that this coupling can be completely controlled by varying the strength of the magnetic field. Finally, we explain these phenomena analytically by mode mixing of the two species via spin-exchange collisions. PMID:26406827

  10. Renal tubular acidosis due to the milk-alkali syndrome.

    PubMed

    Rochman, J; Better, O S; Winaver, J; Chaimowitz, C; Barzilai, A; Jacobs, R

    1977-06-01

    A 60-year-old man with a history of excessive ingestion of calcium carbonate presented with azotemia, hypercalcemia and hyperphosphatemia. His acid-base status was initially normal. Following the cessation of calcium carbonate treatment, the hypercalcemia and azotemia disappeared, and the patient was found to be in metabolic acidosis with blunted acid excretion and a urine pH of 6.1. Kidney biopsy showed focal tubular calcification; the tubular damage was apparently caused by hypercalcemia and had resulted in renal tubular acidosis. During the three months of observation since that time there has been a tendecy for spontaneous remission of the renal tubular acidosis. Impaired renal hydrogen ion excretion prevented the development of metabolic alkalosis despite ingestion of alkali initially, and was later responsible for the metabolic acidosis. Renal tubular acidosis occurring as a sequel to the milk-alkali syndrome may aggravate the danger of nephrocalcinosis in this syndrome. PMID:885714

  11. Operation and performance of a double-alkali scrubber

    SciTech Connect

    Sachtschale, J.R.; Dydo, J.F.

    1982-11-01

    Santa Fe Energy Co. (SFEC) installed a double-alkali sulfur dioxide absorber at its Kern River field near Bakersfield, CA. The flue gas desulfurization (FGD) system is designed to remove 95% of the sulfur dioxide from the exhaust of eight oil-fired steam generators when 1.5 wt% sulfur fuel oil is burned. The chemistry of the double-alkali process and the results of compliance and performance emissions testing are presented. Sulfur dioxide emission results are analyzed. Performance tests showed that total outlet sulfur dioxide emissions were 28.7 lbm/hr (0.00363 kg/s). If offset emissions are included, the net sulfur dioxide emissions were 0.22 lbm/hr (0.00003 kg/s).

  12. Polymerization reactivity of sulfomethylated alkali lignin modified with horseradish peroxidase.

    PubMed

    Yang, Dongjie; Wu, Xiaolei; Qiu, Xueqing; Chang, Yaqi; Lou, Hongming

    2014-03-01

    Alkali lignin (AL) was employed as raw materials in the present study. Sulfomethylation was conducted to improve the solubility of AL, while sulfomethylated alkali lignin (SAL) was further polymerized by horseradish peroxidase (HRP). HRP modification caused a significant increase in molecular weight of SAL which was over 20 times. It was also found to increase the amount of sulfonic and carboxyl groups while decrease the amount of phenolic and methoxyl groups in SAL. The adsorption quantity of self-assembled SAL film was improved after HRP modification. Sulfonation and HRP modification were mutually promoted. The polymerization reactivity of SAL in HRP modification was increased with its sulfonation degree. Meanwhile, HRP modification facilitated SAL's radical-sulfonation reaction. PMID:24534439

  13. Synthesis and studies on microhardness of alkali zinc borate glasses

    NASA Astrophysics Data System (ADS)

    Subhashini, Bhattacharya, Soumalya; Shashikala, H. D.; Udayashankar, N. K.

    2014-04-01

    The mixed alkali effect on zinc borate glasses have been reported. The glass systems of nominal composition 10Zn+xLi2O+yNa2O+80B2O3 (x = y = 0, 5, 10, 15 mol%) were prepared using standard melt quenching method. The structural, physical and mechanical properties of the samples have been studied using X-ray diffraction(XRD), density measurement and Vickers hardness measurement, respectively. A consistent increase in the density was observed, which explains the role of the modifiers (Li2O and Na2O) in the network modification of borate structure. The molar volume is decreasing linearly with the alkali concentration, which is attributed to the conversion of tetrahedral boron (BO4/2)- into (BO3/2)-. The microhardness studies reveals the anisotropy nature of the material. It further confirms that the samples belong to hard glass category.

  14. Optical Properties of Tm(3+) Ions in Alkali Germanate Glass

    NASA Technical Reports Server (NTRS)

    Walsh, Brian M.; Barnes, Norman P.; Reichle, Donald J.; Jiang, Shibin

    2006-01-01

    Tm-doped alkali germanate glass is investigated for use as a laser material. Spectroscopic investigations of bulk Tm-doped germanate glass are reported for the absorption, emission and luminescence decay. Tm:germanate shows promise as a fiber laser when pumped with 0.792 m diodes because of low phonon energies. Spectroscopic analysis indicates low nonradiative quenching and pulsed laser performance studies confirm this prediction by showing a quantum efficiency of 1.69.

  15. Lithological influence of aggregate in the alkali-carbonate reaction

    SciTech Connect

    Lopez-Buendia, A.M. . E-mail: angel.lopez@aidico.es; Climent, V. . E-mail: vcliment@grupogla.com; Verdu, P.

    2006-08-15

    The reactivity of carbonate rock with the alkali content of cement, commonly called alkali-carbonate reaction (ACR), has been investigated. Alkali-silica reaction (ASR) can also contribute in the alkali-aggregate reaction (AAR) in carbonate rock, mainly due to micro- and crypto-crystalline quartz or clay content in carbonate aggregate. Both ACR and ASR can occur in the same system, as has been also evidenced on this paper. Carbonate aggregate samples were selected using lithological reactivity criteria, taking into account the presence of dedolomitization, partial dolomitization, micro- and crypto-crystalline quartz. Selected rocks include calcitic dolostone with chert (CDX), calcitic dolostone with dedolomitization (CDD), limestone with chert (LX), marly calcitic dolostone with partial dolomitization (CD), high-porosity ferric dolostone with clays (FD). To evaluate the reactivity, aggregates were studied using expansion tests following RILEM AAR-2, AAR-5, a modification using LiOH AAR-5Li was also tested. A complementary study was done using petrographic monitoring with polarised light microscopy on aggregates immersed in NaOH and LiOH solutions after different ages. SEM-EDAX has been used to identify the presence of brucite as a product of dedolomitization. An ACR reaction showed shrinkage of the mortar bars in alkaline solutions explained by induced dedolomitization, while an ASR process typically displayed expansion. Neither shrinkage nor expansion was observed when mortar bars were immersed in solutions of lithium hydroxide. Carbonate aggregate classification with AAR pathology risk has been elaborated based on mechanical behaviours by expansion and shrinkage. It is proposed to be used as a petrographic method for AAR diagnosis to complement the RILEM AAR1 specifically for carbonate aggregate. Aggregate materials can be classified as I (non-reactive), II (potentially reactive), and III (probably reactive), considering induced dedolomitization ACR

  16. Precision optical metrology with alkali-atom isoclinic points

    NASA Astrophysics Data System (ADS)

    Wells, Nathan; Driskell, Travis; Camparo, James

    2016-06-01

    Vapour-phase spectroscopy rarely involves transitions between well-isolated atomic states. Routinely, the spectra comprise overlapped Doppler/pressure-broadened resonances, which leads to a “pulling” of the spectral peaks from their true atomic resonance frequencies. This pulling gives the absorption resonances a temperature sensitivity, which limits their utility for precision spectroscopy when sub-Doppler techniques are not viable. Here, we discuss the use of alkali isoclinic points as a solution to this problem.

  17. Resonances in low-energy positron-alkali scattering

    NASA Technical Reports Server (NTRS)

    Horbatsch, M.; Ward, S. J.; Mceachran, R. P.; Stauffer, A. D.

    1990-01-01

    Close-coupling calculations were performed with up to five target states at energies in the excitation threshold region for positron scattering from Li, Na and K. Resonances were discovered in the L = 0, 1 and 2 channels in the vicinity of the atomic excitation thresholds. The widths of these resonances vary between 0.2 and 130 MeV. Evidence was found for the existence of positron-alkali bound states in all cases.

  18. High-energy transversely pumped alkali vapor laser

    NASA Astrophysics Data System (ADS)

    Zweiback, J.; Komashko, A.

    2011-03-01

    We report on the results from our transversely pumped alkali laser. This system uses an Alexandrite laser to pump a stainless steel laser head. The system uses methane and helium as buffer gasses. Using rubidium, the system produced up to 40 mJ of output energy when pumped with 63 mJ. Slope efficiency was 75%. Using potassium as the lasing species the system produced 32 mJ and a 53% slope efficiency.

  19. Diode pumped alkali vapor lasers for high power applications

    NASA Astrophysics Data System (ADS)

    Zweiback, J.; Krupke, B.; Komashko, A.

    2008-02-01

    General Atomics has been engaged in the development of diode pumped alkali vapor lasers. We have been examining the design space looking for designs that are both efficient and easily scalable to high powers. Computationally, we have looked at the effect of pump bandwidth on laser performance. We have also looked at different lasing species. We have used an alexandrite laser to study the relative merits of different designs. We report on the results of our experimental and computational studies.

  20. 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.