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

PubMed

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

2014-07-16

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

Kinetics and Mechanisms of Chemical and Biological Agents Release from Biopolymeric Microcapsules.

PubMed

Vinceković, Marko; Jurić, Slaven; Đermić, Edyta; Topolovec-Pintarić, Snježana

2017-11-08

Kinetics and mechanisms of copper cations and Trichoderma viride spores release from uncoated and chitosan coated alginate microcapsules were investigated. The gelation of a fixed amount of sodium alginate at different concentrations of copper ion solutions resulted in distinct kinetics and release mechanisms. The increase in copper cation concentration promoted, but the presence of the chitosan layer on the microcapsule surface and the increase in microcapsule size reduced the rate of active agent release. Fitting to simple Korsmeyer-Peppas empirical model revealed that the underlying release mechanism (Fickian diffusion or a combination of the diffusion and erosion mechanisms) depends on the copper cation concentration and presence of T. viride spores. The investigation pointed out that the proper selection of formulation variables helps in designing microcapsules with the desirable release of copper ions and T. viride for plant protection and nutrition.

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

DOE PAGES

Uberuaga, Blas Pedro; Perriot, Romain

2015-08-26

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

Carbon Incorporation and Anion Dynamics as Synergistic Drivers for Ultrafast Diffusion in Superionic LiCB 11H 12 and NaCB 11H 12

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

Dimitrievska, Mirjana; Shea, Patrick; Kweon, Kyoung E.

The disordered phases ofLiCB 11H 12 and NaCB 11H 12 possess superb superionic conductivities that make them suitable as solid electrolytes. In these materials, cation diffusion correlates with high orientational mobilities of the CB 11H 12 - anions; however, the precise relationship has yet to be demonstrated. In this work, ab initio molecular dynamics and quasielastic neutron scattering are combined to probe anion reorientations and their mechanistic connection to cation mobility over a range of timescales and temperatures. It is found that anions do not rotate freely, but rather transition rapidly between orientations defined by the cation sublattice symmetry. Themore » symmetry-breaking carbon atom in CB 11H 12 - also plays a critical role by perturbing the energy landscape along the instantaneous orientation of the anion dipole, which couples fluctuations in the cation probability density directly to the anion motion. Anion reorientation rates exceed 3 x 10 10 s -1, suggesting the underlying energy landscape fluctuates dynamically on diffusion-relevant timescales. Furthermore, carbon is found to modify the orientational preferences of the anions and aid rotational mobility, creating additional symmetry incompatibilities that inhibit ordering. The results suggest that synergy between the anion reorientational dynamics and the carbon-modified cation-anion interaction accounts for the higher ionic conductivity in CB 11H 12 - salts compared with B 12H 12 2-.« less

Carbon Incorporation and Anion Dynamics as Synergistic Drivers for Ultrafast Diffusion in Superionic LiCB 11H 12 and NaCB 11H 12

DOE PAGES

Dimitrievska, Mirjana; Shea, Patrick; Kweon, Kyoung E.; ...

2018-02-20

The disordered phases ofLiCB 11H 12 and NaCB 11H 12 possess superb superionic conductivities that make them suitable as solid electrolytes. In these materials, cation diffusion correlates with high orientational mobilities of the CB 11H 12 - anions; however, the precise relationship has yet to be demonstrated. In this work, ab initio molecular dynamics and quasielastic neutron scattering are combined to probe anion reorientations and their mechanistic connection to cation mobility over a range of timescales and temperatures. It is found that anions do not rotate freely, but rather transition rapidly between orientations defined by the cation sublattice symmetry. Themore » symmetry-breaking carbon atom in CB 11H 12 - also plays a critical role by perturbing the energy landscape along the instantaneous orientation of the anion dipole, which couples fluctuations in the cation probability density directly to the anion motion. Anion reorientation rates exceed 3 x 10 10 s -1, suggesting the underlying energy landscape fluctuates dynamically on diffusion-relevant timescales. Furthermore, carbon is found to modify the orientational preferences of the anions and aid rotational mobility, creating additional symmetry incompatibilities that inhibit ordering. The results suggest that synergy between the anion reorientational dynamics and the carbon-modified cation-anion interaction accounts for the higher ionic conductivity in CB 11H 12 - salts compared with B 12H 12 2-.« less

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

PubMed

Chakraborty, Brahmananda

2015-08-20

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

Nuclear magnetic resonance investigation of dynamics in poly(ethylene oxide) based polyether-ester-sulfonate ionomers

NASA Astrophysics Data System (ADS)

Roach, David J.

Nuclear magnetic resonance (NMR) spectroscopy has been utilized to investigate the dynamics of poly(ethylene oxide)-based lithium sulfonate ionomer samples that have low glass transition temperatures. 1H and 7Li spin-lattice relaxation times (T1) of the bulk polymer and lithium ions, respectively, were measured and analyzed in samples with a range of ion contents. The temperature dependence of T1 values along with the presence of minima in T1 as a function of temperature enabled correlation times and activation energies to be obtained for both the segmental motion of the polymer backbone and the hopping motion of lithium cations. Similar activation energies for motion of both the polymer and lithium ions in the samples with lower ion content indicate that the polymer segmental motion and lithium ion hopping motion are correlated in these samples, even though lithium hopping is about ten times slower than the segmental motion. A divergent trend is observed for correlation times and activation energies of the highest ion content sample with 100% lithium sulfonation due to the presence of ionic aggregation. Details of the polymer and cation dynamics on the nanosecond timescale are discussed and complement the findings of X-ray scattering and Quasi Elastic Neutron Scattering experiments. Polymer backbone dynamics of single ion conducting poly(ethylene oxide) (PEO)-based ionomer samples with low glass transition temperatures (T g) have been investigated using solid-state nuclear magnetic resonance (NMR). Experiments detecting 13C with 1H decoupling under magic angle spinning (MAS) conditions identified the different components and relative mobilities of the polymer backbone of a suite of. lithium- and sodium-containing ionomer samples with varying cation contents. Variable temperature (203-373 K) 1H-13C cross-polarization MAS (CP-MAS) experiments also provided qualitative assessment of the differences in the motions of the polymer backbone components as a function of cation content. Each of the main backbone components (PEO spacer and isophthalate groups) exhibit distinct motions, following the trends expected for motional characteristics based on earlier Quasi Elastic Neutron Scattering and 1H spin-lattice relaxation rate measurements. The temperature dependences of 13C linewidths were used to both qualitatively and quantitatively examine the effects of cation content on PEO mobility. Variable contact time 1H-13C CP-MAS experiments were used to further assess the motions of the polymer backbone on the microsecond timescale. The motion of the PEO spacer, determined from the rate of magnetization transfer from 1H to 13C nuclei, in all ionic samples becomes similar for T [special characters omitted] 1.1 Tg, indicating that the motions of the polymer backbones on the microsecond timescale become insensitive to ion interactions. These results compliment previous findings and present an improved picture of the dependence of backbone dynamics on cation type and density in these amorphous PEO-based ionomer systems. 7Li PFG NMR experiments provided measurements of the self-diffusion coefficients for Li+ cations in the PEO600-y Li ionomer series over a range of temperatures. When the Tg values are taken into account, the self-diffusion coefficients of Li+ in each sample follow a similar trendline, indicating that lithium diffusion is independent of ion concentration at any given reduced inverse temperature, Tg/T. Ion aggregation increases Tg and slows both lithium cation diffusion and displacement, but there is no further slowing beyond the Tg effect in the PEO600-y Li ionomers samples. The differences in activation energies obtained from diffusion measurements and relaxation times suggest that at least one additional barrier must be overcome for cations emerge from local hopping motion to macroscopic cation transpfort. Using the Nernst- Einstein equation lithium diffusion coefficients were also calculated from conductivity measurements. The differences between the diffusion measured by the two separate techniques indicate the presence of ion pairs. The activation energy of lithium diffusion was found to be nearly identical between the PFG NMR and conductivity, suggesting that the conductivity and ionic diffusion are related to the same ionic dynamics. As the ion content within the PEO600-y Li samples increases the relative concentration of nonconducting ion pairs decrease. Also an increase in temperature causes a fraction of ion pairs to thermally dissociate into positive triple ions.

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

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

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

2015-05-15

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

Photoinduced Bimolecular Electron Transfer in Ionic Liquids: Cationic Electron Donors

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

Wu, Boning; Liang, Min; Zmich, Nicole

Recently, we have reported a systematic study of photoinduced electron-transfer reactions in ionic liquid solvents using neutral and anionic electron donors and a series of cyano-substituted anthracene acceptors [Wu, B.; Maroncelli, M.; Castner, E. W., Jr.Photoinduced Bimolecular Electron Transfer in Ionic Liquids. J. Am. Chem. Soc.139, 2017, 14568]. In this paper, we report complementary results for a cationic class of 1-alkyl-4-dimethylaminopyridinium electron donors. Reductive quenching of cyano-substituted anthracene fluorophores by these cationic quenchers is studied in solutions of acetonitrile and the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Varying the length of the alkyl chain permits tuning of the quencher diffusivities in solution.more » The observed quenching kinetics are interpreted using a diffusion-reaction analysis. Finally, together with results from the prior study, these results show that the intrinsic electron-transfer rate constant does not depend on the quencher charge in this family of reactions.« less

Effect of Aprotic Solvents on the Dynamics of a Room Temperature Ionic Liquid

NASA Astrophysics Data System (ADS)

Osti, Naresh; van Aken, Katherine; Thompson, Matthew; Tiet, Felix; Jiang, De-En; Cummings, Peter; Gogotsi, Yury; Mamontov, Eugene

Room temperature ionic liquids (RTILs) have attracted much attention as electrolytes in energy storage devices because of their peculiar physical and chemical characteristics. However, their remarkably high viscosity, which results in low conductivity and diffusivity, may adversely affect the charging and discharging rates. Despite changing molecular configurations, use of aprotic solvent allows to enhance the transport properties of ionic liquids by disrupting the cation-anion interactions. We explore the impact of dipole moment of aprotic solvents on the cation-anion interaction and transport in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [BMIM +][Tf2N-], RTIL using molecular dynamics (MD) simulations and quasi-elastic neutrons scattering (QENS) measurements. We observed an increase in cation diffusivity with the increasing dipole moment of the solvent. This effect is due to a decrease in the solvation free energy induced by the increasing solvent polarity. A clear nano-phase separation into ionic liquid-rich and ionic liquid-poor phases as observed by QENS will be also discussed.

Photoinduced Bimolecular Electron Transfer in Ionic Liquids: Cationic Electron Donors

DOE PAGES

Wu, Boning; Liang, Min; Zmich, Nicole; ...

2018-01-29

Recently, we have reported a systematic study of photoinduced electron-transfer reactions in ionic liquid solvents using neutral and anionic electron donors and a series of cyano-substituted anthracene acceptors [Wu, B.; Maroncelli, M.; Castner, E. W., Jr.Photoinduced Bimolecular Electron Transfer in Ionic Liquids. J. Am. Chem. Soc.139, 2017, 14568]. In this paper, we report complementary results for a cationic class of 1-alkyl-4-dimethylaminopyridinium electron donors. Reductive quenching of cyano-substituted anthracene fluorophores by these cationic quenchers is studied in solutions of acetonitrile and the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Varying the length of the alkyl chain permits tuning of the quencher diffusivities in solution.more » The observed quenching kinetics are interpreted using a diffusion-reaction analysis. Finally, together with results from the prior study, these results show that the intrinsic electron-transfer rate constant does not depend on the quencher charge in this family of reactions.« less

Simultaneous Extraction of Lithium and Hydrogen from Seawater

DTIC Science & Technology

2011-08-22

to the anode and cathode were determined by ion chromatography . Anions were analyzed by Anion Ion Chromatography (Instrument Dionex ICS-1500, Column...and oxygen gases coming out of the cell were collected and the amount was measured volumetrically. Ion chromatography : Ions in seawater diffused from... Dionex AS9-HC; AG9-HC Guard, eluent: 9.00 mM Na2CO3, flow rate: 1.25 mL/min, and sample loop was 25 μL). Cations were analyzed by Cation Ion

Empirical constraints on closure temperatures from a single diffusion coefficient

NASA Astrophysics Data System (ADS)

Lee, J. K. W.

The elucidation of thermal histories by geochronological and isotopic means is based fundamentally on solid-state diffusion and the concept of closure temperatures. Because diffusion is thermally activated, an analytical solution of the closure temperature (Tc*) can only be obtained if the diffusion coefficient D of the diffusion process is measured at two or more different temperatures. If the diffusion coefficient is known at only one temperature, however, the true closure temperature (Tc*) cannot be calculated analytically because there exist an infinite number of possible (apparent) closure temperatures (Tc) which can be generated by this single datum. By introducing further empirical constraints to limit the range of possible closure temperatures, however, mathematical analysis of a modified form of the closure temperature equation shows that it is possible to make both qualitative and quantitative estimates of Tc* given knowledge of only one diffusion coefficient DM measured at one temperature TM. Qualitative constraints of the true closure temperature Tc* are obtained from the shapes of curves on a graph of the apparent Tc (Tc) vs. activation energy E, in which each curve is based on a single diffusion coefficient measurement DM at temperature TM. Using a realistic range of E, the concavity of the curve shows whether TM is less than, approximately equal to, or greater than Tc*. Quantitative estimates are obtained by considering two dimensionless parameters [lnÊRT^c vs. Tc*/TM] derived from these curves. When these parameters are plotted for known argon diffusion data and for a given diffusion size and cooling rate, it is found that the resultant curves are almost identical for all of the commonly dated K-Ar minerals - biotite, phlogopite, muscovite, hornblende and orthoclase - in spite of differences in their diffusion parameters. A common curve for Ar diffusion can be derived by least-squares fitting of all the Ar diffusion data and provides a way of predicting a ``model'' closure temperature Tcm from a single diffusion coefficient DM at temperature TM. Preliminary diffusion data for a labradorite lead to a Tcm of 507+/-17°C and a corresponding activation energy of about 65kcal/mol, given a grain size of 200μm and a cooling rate of 5°C/Ma. Curves for He diffusion in silicates (augite, quartz and sanidine) also overlap to a significant degree, both among themselves and with the Ar model curve, suggesting that a single model curve may be a good representation of noble gas closure temperatures in silicates. An analogous model curve for a selection of 18O data can also be constructed, but this curve differs from the Ar model curve. A single model curve for cationic species does not appear to exist, however, suggesting that chemical bonding relationships between the ionic size/charge and crystal structure may influence the closure temperatures of diffusing cations. An indication of the degree of overlap among the various curves for Ar, He, 18O and cations is also obtained by considering the dimensionless parameter E/RTc*; for the noble gases and 18O, E/RTc* values for the respective minerals are very similar, whereas for cations, there is significant dispersion. Given these constraints, this may be a potential method of estimating closure temperatures for certain diffusing species when there are limited diffusion data.

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

PubMed

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

2008-12-14

Molecular dynamics simulations are used to study the dynamics and transport properties of 12 room-temperature ionic liquids of the 1-alkyl-3-methylimidazolium [amim](+) (alkyl = methyl, ethyl, propyl, and butyl) family with PF(6)(-), NO(3)(-), and Cl(-) counterions. The explicit atom transferable force field of Canongia Lopes et al. [J. Phys. Chem. B 108, 2038 (2004)] is used in the simulations. In this first part, the dynamics of the ionic liquids are characterized by studying the mean-square displacement (MSD) and the velocity autocorrelation function (VACF) for the centers of mass of the ions at 400 K. Trajectory averaging was employed to evaluate the diffusion coefficients at two temperatures from the linear slope of MSD(t) functions in the range of 150-300 ps and from the integration of the VACF(t) functions at 400 K. Detailed comparisons are made between the diffusion results from the MSD and VACF methods. The diffusion coefficients from the integration of the VACFs are closer to experimental values than the diffusion coefficients calculated from the slope of MSDs. Both methods can show good agreement with experiment in predicting relative trends in the diffusion coefficients and determining the role of the cation and anion structures on the dynamical behavior of this family of ionic liquids. The MSD and self-diffusion of relatively heavier imidazolium cations are larger than those of the lighter anions from the Einstein results, except for the case of [bmim][Cl]. The cationic transference number generally decreases with temperature, in good agreement with experiments. For the same anion, the cationic transference numbers decrease with increasing length of the alkyl chain, and for the same cation, the trends in the cationic transference numbers are [NO(3)](-) < [Cl](-) < [PF(6)](-). The trends in the diffusion coefficient in the series of cations with identical anions are [emim](+) > [pmim](+) > [bmim](+) and those for anions with identical cations are [NO(3)](-) > [PF(6)](-) > [Cl](-). The [dmim](+) has a relatively low diffusion coefficient due to its symmetric structure and good packing in the liquid phase. The major factor for determining the magnitude of the self-diffusion is the geometric shape of the anion of the ionic liquid. Other important factors are the ion size and the charge delocalization in the anion.

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

NASA Technical Reports Server (NTRS)

Good, Brian

2013-01-01

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

Thermodynamics and Cation Diffusion in the Oxygen Ion Conductor Lsgm

NASA Astrophysics Data System (ADS)

Martin, M.; Schulz, O.

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

Two-cation competition in ionic-liquid-modified electrolytes for lithium ion batteries.

PubMed

Lee, Sang-Young; Yong, Hyun Hang; Lee, Young Joo; Kim, Seok Koo; Ahn, Soonho

2005-07-21

It is a common observation that when ionic liquids are added to electrolytes the performances of lithium ion cells become poor, while the thermal safeties of the electrolytes might be improved. In this study, this behavior is investigated based on the kinetics of ionic diffusion. As a model ionic liquid, we chose butyldimethylimidazolium hexafluorophosphate (BDMIPF(6)). The common solvent was propylene carbonate (PC), and lithium hexafluorophosphate (LiPF(6)) was selected as the lithium conducting salt. Ionic diffusion coefficients are estimated by using a pulsed field gradient NMR technique. From a basic study on the model electrolytes (BDMIPF(6) in PC, LiPF(6) in PC, and BDMIPF(6) + LiPF(6) in PC), it was found that the BDMI(+) from BDMIPF(6) shows larger diffusion coefficients than the Li(+) from LiPF(6). However, the anionic (PF(6)(-)) diffusion coefficients present little difference between the model electrolytes. The higher diffusion coefficient of BDMI(+) than that of Li(+) suggests that the poor C-rate performance of lithium ion cells containing ionic liquids as an electrolyte component can be attributed to the two-cation competition between Li(+) and BDMI(+).

NMR Water Self–Diffusion and Relaxation Studies on Sodium Polyacrylate Solutions and Gels in Physiologic Ionic Solutions

PubMed Central

Bai, Ruiliang; Basser, Peter J.; Briber, Robert M.; Horkay, Ferenc

2013-01-01

Water self-diffusion coefficients and longitudinal relaxation rates in sodium polyacrylate solutions and gels were measured by NMR, as a function of polymer content and structure in a physiological concentration range of monovalent and divalent cations, Ca2+ and Na+. Several physical models describing the self-diffusion of the solvent were applied and compared. A free-volume model was found to be in good agreement with the experimental results over a wide range of polymer concentrations. The longitudinal relaxation rate exhibited linear dependence on polymer concentration below a critical concentration and showed non-linear behavior at higher concentrations. Both the water self-diffusion and relaxation were less influenced by the polymer in the gel state than in the uncrosslinked polymer solutions. The effect of Na+ on the mobility of water molecules was practically undetectable. By contrast, addition of Ca2+ strongly increased the longitudinal relaxation rate while its effect on the self-diffusion coefficient was much less pronounced. PMID:24409001

NMR Water Self-Diffusion and Relaxation Studies on Sodium Polyacrylate Solutions and Gels in Physiologic Ionic Solutions.

PubMed

Bai, Ruiliang; Basser, Peter J; Briber, Robert M; Horkay, Ferenc

2014-03-15

Water self-diffusion coefficients and longitudinal relaxation rates in sodium polyacrylate solutions and gels were measured by NMR, as a function of polymer content and structure in a physiological concentration range of monovalent and divalent cations, Ca 2+ and Na + . Several physical models describing the self-diffusion of the solvent were applied and compared. A free-volume model was found to be in good agreement with the experimental results over a wide range of polymer concentrations. The longitudinal relaxation rate exhibited linear dependence on polymer concentration below a critical concentration and showed non-linear behavior at higher concentrations. Both the water self-diffusion and relaxation were less influenced by the polymer in the gel state than in the uncrosslinked polymer solutions. The effect of Na + on the mobility of water molecules was practically undetectable. By contrast, addition of Ca 2+ strongly increased the longitudinal relaxation rate while its effect on the self-diffusion coefficient was much less pronounced.

Influence of humidity on performance and microscopic dynamics of an ionic liquid in supercapacitor

NASA Astrophysics Data System (ADS)

Osti, Naresh C.; Dyatkin, Boris; Thompson, Matthew W.; Tiet, Felix; Zhang, Pengfei; Dai, Sheng; Tyagi, Madhusudan; Cummings, Peter T.; Gogotsi, Yury; Wesolowski, David J.; Mamontov, Eugene

2017-08-01

We investigated the influence of water molecules on the diffusion, dynamics, and electrosorption of a room temperature ionic liquid (RTIL), [BMI m+] [T f2N-] , confined in carbide-derived carbon with a bimodal nanoporosity. Water molecules in pores improved power densities and rate handling abilities of these materials in supercapacitor electrode configurations. We measured the water-dependent microscopic dynamics of the RTIL cations using quasielastic neutron scatting (QENS). The ionic liquid demonstrated greater mobility with increasing water uptake, facilitated by the nanoporous carbon environment, up to a well-defined saturation point. We concluded that water molecules displaced RTIL ions attached to the pore surfaces and improved the diffusivity of the displaced cations. This effect consequently increased capacitance and rate handling of the electrolyte in water-containing pores. Our findings suggest the possible effect of immiscible co-solvents on energy and power densities of energy storage devices, as well as the operating viability of nonaqueous supercapacitor electrolytes in humid environments.

Anomalous cation diffusion in salt-doped confined bilayer ice.

PubMed

Qiu, Hu; Xue, Minmin; Shen, Chun; Guo, Wanlin

2018-05-17

The diffusive dynamics of aqueous electrolyte solutions in nanoconfined spaces has attracted considerable attention due to their potential applications in desalination, biosensors and supercapacitors. Here we show by molecular dynamics simulations that lithium and sodium ions diffuse at a rate at least an order of magnitude higher than that of water molecules when the ions are trapped in an ice bilayer confined between two parallel plates. This novel picture is in sharp contrast to the prevailing view that the diffusion rate of ions is comparable to or even lower than that of water in both bulk and confined solutions. The predicted high ion mobility stems from frequent lateral hopping of ions along the coordination sites inside the hydrogen-bonding network connecting the two water layers of the ice bilayer. This anomalous diffusion should provide new insights into the physics of confined aqueous electrolytes.

Ion Pairing and Diffusion in Magnesium Electrolytes Based on Magnesium Borohydride.

PubMed

Samuel, Devon; Steinhauser, Carl; Smith, Jeffrey G; Kaufman, Aaron; Radin, Maxwell D; Naruse, Junichi; Hiramatsu, Hidehiko; Siegel, Donald J

2017-12-20

One obstacle to realizing a practical, rechargeable magnesium-ion battery is the development of efficient Mg electrolytes. Electrolytes based on simple Mg(BH 4 ) 2 salts suffer from poor salt solubility and/or low conductivity, presumably due to strong ion pairing. Understanding the molecular-scale processes occurring in these electrolytes would aid in overcoming these performance limitations. Toward this goal, the present study examines the solvation, agglomeration, and transport properties of a family of Mg electrolytes based on the Mg(BH 4 ) 2 salt using classical molecular dynamics. These properties were examined across five different solvents (tetrahydrofuran and the glymes G1-G4) and at four salt concentrations ranging from the dilute limit up to 0.4 M. Significant and irreversible salt agglomeration was observed in all solvents at all nondilute Mg(BH 4 ) 2 concentrations. The degree of clustering observed in these divalent Mg systems is much larger than that reported for electrolytes containing monovalent cations, such as Li. The salt agglomeration rate and diffusivity of Mg 2+ were both observed to correlate with solvent self-diffusivity: electrolytes using longer- (shorter-) chain solvents had the lowest (highest) Mg 2+ diffusivity and agglomeration rates. Incorporation of Mg 2+ into Mg 2+ -BH 4 - clusters significantly reduces the diffusivity of Mg 2+ by restricting displacements to localized motion within largely immobile agglomerates. Consequently, diffusion is increasingly impeded with increasing Mg(BH 4 ) 2 concentration. These data are consistent with the solubility limitations observed experimentally for Mg(BH 4 ) 2 -based electrolytes and highlight the need for strategies that minimize salt agglomeration in electrolytes containing divalent cations.

Nanoscale oxidation and complex oxide growth on single crystal iron surfaces and external electric field effects.

PubMed

Jeon, Byoungseon; Van Overmeere, Quentin; van Duin, Adri C T; Ramanathan, Shriram

2013-02-14

Oxidation of iron surfaces and oxide growth mechanisms have been studied using reactive molecular dynamics. Oxide growth kinetics on Fe(100), (110), and (111) surface orientations has been investigated at various temperatures and/or an external electric field. The oxide growth kinetics decreases in the order of (110), (111), and (100) surfaces at 300 K over 1 ns timescale while higher temperature increases the oxidation rate. The oxidation rate shows a transition after an initial high rate, implying that the oxide formation mechanism evolves, with iron cation re-ordering. In early stages of surface oxide growth, oxygen transport through iron interstitial sites is dominant, yielding non-stoichiometric wüstite characteristics. The dominant oxygen inward transport decreases as the oxide thickens, evolving into more stoichiometric oxide phases such as wüstite or hematite. This also suggests that cation outward transport increases correspondingly. In addition to oxidation kinetics simulations, formed oxide layers have been relaxed in the range of 600-1500 K to investigate diffusion characteristics, fitting these results into an Arrhenius relation. The activation energy of oxygen diffusion in oxide layers formed on Fe(100), (110), and (111) surfaces was estimated to be 0.32, 0.26, and 0.28 eV, respectively. Comparison between our modeling results and literature data is then discussed. An external electric field (10 MV cm(-1)) facilitates initial oxidation kinetics by promoting oxygen transport through iron lattice interstitial sites, but reaches self-limiting thickness, showing that similar oxide formation stages are maintained when cation transport increases. The effect of the external electric field on iron oxide structure, composition, and oxide activation energy is found to be minimal, whereas cation outward migration is slightly promoted.

Relation between heat of vaporization, ion transport, molar volume, and cation-anion binding energy for ionic liquids.

PubMed

Borodin, Oleg

2009-09-10

A number of correlations between heat of vaporization (H(vap)), cation-anion binding energy (E(+/-)), molar volume (V(m)), self-diffusion coefficient (D), and ionic conductivity for 29 ionic liquids have been investigated using molecular dynamics (MD) simulations that employed accurate and validated many-body polarizable force fields. A significant correlation between D and H(vap) has been found, while the best correlation was found for -log(DV(m)) vs H(vap) + 0.28E(+/-). A combination of enthalpy of vaporization and a fraction of the cation-anion binding energy was suggested as a measure of the effective cohesive energy for ionic liquids. A deviation of some ILs from the reported master curve is explained based upon ion packing and proposed diffusion pathways. No general correlations were found between the ion diffusion coefficient and molecular volume or the diffusion coefficient and cation/anion binding energy.

Enhancing Cation Diffusion and Suppressing Anion Diffusion via Lewis-Acidic Polymer Electrolytes.

PubMed

Savoie, Brett M; Webb, Michael A; Miller, Thomas F

2017-02-02

Solid polymer electrolytes (SPEs) have the potential to increase both the energy density and stability of lithium-based batteries, but low Li + conductivity remains a barrier to technological viability. SPEs are designed to maximize Li + diffusivity relative to the anion while maintaining sufficient salt solubility. It is thus remarkable that poly(ethylene oxide) (PEO), the most widely used SPE, exhibits Li + diffusivity that is an order of magnitude smaller than that of typical counterions at moderate salt concentrations. We show that Lewis-basic polymers like PEO favor slow cation and rapid anion diffusion, while this relationship can be reversed in Lewis-acidic polymers. Using molecular dynamics, polyboranes are identified that achieve up to 10-fold increases in Li + diffusivities and significant decreases in anion diffusivities, relative to PEO in the dilute-ion regime. These results illustrate a general principle for increasing Li + diffusivity and transference number with chemistries that exhibit weaker cation and stronger anion coordination.

The diffusion dynamics of PEGylated liposomes in the intact vitreous of the ex vivo porcine eye: A fluorescence correlation spectroscopy and biodistribution study.

PubMed

Eriksen, Anne Z; Brewer, Jonathan; Andresen, Thomas L; Urquhart, Andrew J

2017-04-30

The diffusion dynamics of nanocarriers in the vitreous and the influence of nanocarrier physicochemical properties on these dynamics is an important aspect of the efficacy of intravitreal administered nanomedicines for the treatment of posterior segment eye diseases. Here we use fluorescence correlation spectroscopy (FCS) to determine liposome diffusion coefficients in the intact vitreous (D Vit ) of ex vivo porcine eyes using a modified Miyake-Apple technique to minimize the disruption of the vitreous fine structure. We chose to investigate whether the zeta potential of polyethylene glycol functionalized (i.e. PEGylated) liposomes altered liposome in situ diffusion dynamics in the vitreous. Non-PEGylated cationic nanocarriers have previously shown little to no diffusion in the vitreous, whilst neutral and anionic have shown diffusion. The liposomes investigated had diameters below 150nm and zeta potentials ranging from -20 to +12mV. We observed that PEGylated cationic liposomes had significantly lower D Vit values (1.14μm 2 s -1 ) than PEGylated neutral and anionic liposomes (2.78 and 2.87μm 2 s -1 ). However, PEGylated cationic liposomes had a similar biodistribution profile across the vitreous to the other systems. These results show that PEGylated cationic liposomes with limited cationic charge can diffuse across the vitreous and indicate that the vitreous as a barrier to nanocarriers (Ø<500nm) is more complicated than simply an electrostatic barrier as previously suggested. Copyright © 2017 Elsevier B.V. All rights reserved.

Bipolar membranes with fluid distribution passages

NASA Technical Reports Server (NTRS)

Hitchens, G. Duncan (Inventor); Archer, Shivaun (Inventor); Tennakoon, Charles L. (Inventor); Gonzalez-Martin, Anuncia (Inventor); Cisar, Alan J. (Inventor)

1999-01-01

The present invention provides a bipolar membrane and methods for making and using the membrane. The bipolar membrane comprises a cation-selective region, an anion-selective region, an interfacial region between the anion-selective region and the cation-selective region, and means for delivering fluid directly into the interfacial region. The means for delivering fluid includes passages that may comprise a fluid-permeable material, a wicking material, an open passage disposed within the membrane or some combination thereof. The passages may be provided in many shapes, sizes and configurations, but preferably deliver fluid directly to the interfacial region so that the rate of electrodialysis is no longer limited by the diffusion of fluid through the cation- or anion-selective regions to the interfacial region.

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

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

Lobnig, R.E.; Hennesen, K.; Grabke, H.J.

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

Diffusion of neutral and ionic species in charged membranes: boric acid, arsenite, and water.

PubMed

Goli, Esmaiel; Hiemstra, Tjisse; Van Riemsdijk, Willem H; Rahnemaie, Rasoul; Malakouti, Mohammad Jafar

2010-10-15

Dynamic ion speciation using DMT (Donnan membrane technique) requires insight into the physicochemical characteristics of diffusion in charged membranes (tortuosity, local diffusion coefficients) as well as ion accumulation. The latter can be precluded by studying the diffusion of neutral species, such as boric acid, B(OH)₃⁰(aq), arsenite, As(OH)₃⁰(aq), or water. In this study, the diffusion rate of B(OH)₃⁰ has been evaluated as a function of the concentration, pH, and ionic strength. The rate is linearly dependent on the concentration of solely the neutral species, without a significant contribution of negatively charged species such as B(OH)₄⁻, present at high pH. A striking finding is the very strong effect (factor of ~10) of the type of cation (K(+), Na(+), Ca(2+), Mg(2+), Al(3+), and H(+)) on the diffusion coefficient of B(OH)₃⁰ and also As(OH)₃⁰. The decrease of the diffusion coefficient can be rationalized as an enhancement of the mean viscosity of the confined solution in the membrane. The diffusion coefficients can be described by a semiempirical relationship, linking the mean viscosity of the confined solute of the membrane to the viscosity of the free solution. In proton-saturated membranes, as used in fuel cells, viscosity is relatively more enhanced; i.e., a stronger water network is formed. Extraordinarily, our B(OH)₃-calibrated model (in HNO₃) correctly predicts the reported diffusion coefficient of water (D(H₂O)), measured with ¹H NMR and quasi-elastic neutron scattering in H(+)-Nafion membranes. Upon drying these membranes, the local hydronium, H(H₂O)(n)(+), concentration and corresponding viscosity increase, resulting in a severe reduction of the diffusion coefficient (D(H₂O) ≈ 5-50 times), in agreement with the model. The present study has a second goal, i.e., development of the methodology for measuring the free concentration of neutral species in solution. Our data suggest that the free concentration can be measured with DMT in natural systems if one accounts for the variation in the cation composition of the membrane and corresponding viscosity/diffusion coefficient.

Electrochemical evidences and consequences of significant differences in ions diffusion rate in polyacrylate-based ion-selective membranes.

PubMed

Woźnica, Emilia; Mieczkowski, Józef; Michalska, Agata

2011-11-21

The origin and effect of surface accumulation of primary ions within the ion-selective poly(n-butyl acrylate)-based membrane, obtained by thermal polymerization, is discussed. Using a new method, based on the relation between the shape of a potentiometric plot and preconditioning time, the diffusion of copper ions in the membrane was found to be slow (the diffusion coefficient estimated to be close to 10(-11) cm(2) s(-1)), especially when compared to ion-exchanger counter ions--sodium cations diffusion (a diffusion coefficient above 10(-9) cm(2) s(-1)). The higher mobility of sodium ions than those of the copper-ionophore complex results in exposed ion-exchanger role leading to undesirably exposed sensitivity to sodium or potassium ions.

Molecular dynamics simulation of diffusion and electrical conductivity in montmorillonite interlayers

DOE PAGES

Greathouse, Jeffery A.; Cygan, Randall T.; Fredrich, Joanne T.; ...

2016-01-20

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

Dependence of Ion Dynamics on the Polymer Chain Length in Poly(ethylene oxide)-Based Polymer Electrolytes.

PubMed

Chattoraj, Joyjit; Knappe, Marisa; Heuer, Andreas

2015-06-04

It is known from experiments that in the polymer electrolyte system, which contains poly(ethylene oxide) chains (PEO), lithium-cations (Li(+)), and bis(trifluoromethanesulfonyl)imide-anions (TFSI(-)), the cation and the anion diffusion and the ionic conductivity exhibit a similar chain-length dependence: with increasing chain length, they start dropping steadily, and later, they saturate to constant values. These results are surprising because Li-cations are strongly correlated with the polymer chains, whereas TFSI-anions do not have such bonding. To understand this phenomenon, we perform molecular dynamics simulations of this system for four different polymer chain lengths. The diffusion results obtained from our simulations display excellent agreement with the experimental data. The cation transport model based on the Rouse dynamics can successfully quantify the Li-diffusion results, which correlates Li diffusion with the polymer center-of-mass motion and the polymer segmental motion. The ionic conductivity as a function of the chain length is then estimated based on the chain-length-dependent ion diffusion, which shows a temperature-dependent deviation for short chain lengths. We argue that in the first regime, counterion correlations modify the conductivity, whereas for the long chains, the system behaves as a strong electrolyte.

Dissolution kinetics of a lunar glass simulant at 25 degrees C: the effect of pH and organic acids

NASA Technical Reports Server (NTRS)

Eick, M. J.; Grossl, P. R.; Golden, D. C.; Sparks, D. L.; Ming, D. W.

1996-01-01

The dissolution kinetics of a simulated lunar glass were examined at pH 3, 5, and 7. Additionally, the pH 7 experiments were conducted in the presence of citric and oxalic acid at concentrations of 2 and 20 mM. The organic acids were buffered at pH 7 to examine the effect of each molecule in their dissociated form. At pH 3, 5, and 7, the dissolution of the synthetic lunar glass was observed to proceed via a two-stage process. The first stage involved the parabolic release of Ca, Mg, Al, and Fe, and the linear release of Si. Dissolution was incongruent, creating a leached layer rich in Si and Ti which was verified by transmission electron microscopy (TEM). During the second stage the release of Ca, Mg, Al, and Fe was linear. A coupled diffusion/surface dissolution model was proposed for dissolution of the simulated lunar glass at pH 3, 5, and 7. During the first stage the initial release of mobile cations (i.e., Ca, Mg, Al, Fe) was limited by diffusion through the surface leached layer of the glass (parabolic release), while Si release was controlled by the hydrolysis of the Si-O-Al bonds at the glass surface (linear release). As dissolution continued, the mobile cations diffused from greater depths within the glass surface. A steady-state was then reached where the diffusion rate across the increased path lengths equalled the Si release rate from the surface. In the presence of the organic acids, the dissolution of the synthetic lunar glass proceeded by a one stage process. The release of Ca, Mg, Al, and Fe followed a parabolic relationship, while the release of Si was linear. The relative reactivity of the organic acids used in the experiments was citrate > oxalate. A thinner leached layer rich in Si/Ti, as compared to the pH experiments, was observed using TEM. Rate data suggest that the chemisorption of the organic anion to the surface silanol groups was responsible for enhanced dissolution in the presence of the organic acids. It is proposed that the increased rate of Si release is responsible for the one stage parabolic release of mobile cations and the relatively thin leached layer compared to experiments at pH 3 and 5.

Competitive separation of di- vs. mono-valent cations in electrodialysis: effects of the boundary layer properties.

PubMed

Kim, Younggy; Walker, W Shane; Lawler, Desmond F

2012-05-01

In electrodialysis desalination, the boundary layer near ion-exchange membranes is the limiting region for the overall rate of ionic separation due to concentration polarization over tens of micrometers in that layer. Under high current conditions, this sharp concentration gradient, creating substantial ionic diffusion, can drive a preferential separation for certain ions depending on their concentration and diffusivity in the solution. Thus, this study tested a hypothesis that the boundary layer affects the competitive transport between di- and mono-valent cations, which is known to be governed primarily by the partitioning with cation-exchange membranes. A laboratory-scale electrodialyzer was operated at steady state with a mixture of 10mM KCl and 10mM CaCl(2) at various flow rates. Increased flows increased the relative calcium transport. A two-dimensional model was built with analytical solutions of the Nernst-Planck equation. In the model, the boundary layer thickness was considered as a random variable defined with three statistical parameters: mean, standard deviation, and correlation coefficient between the thicknesses of the two boundary layers facing across a spacer. Model simulations with the Monte Carlo method found that a greater calcium separation was achieved with a smaller mean, greater standard deviation, or more negative correlation coefficient. The model and experimental results were compared for the cationic transport number as well as the current and potential relationship. The mean boundary layer thickness was found to decrease from 40 to less than 10 μm as the superficial water velocity increased from 1.06 to 4.24 cm/s. The standard deviation was greater than the mean thickness at slower water velocities and smaller at faster water velocities. Copyright © 2012 Elsevier Ltd. All rights reserved.

Theoretical and experimental studies of water interaction in acetate based ionic liquids.

PubMed

Shi, Wei; Damodaran, Krishnan; Nulwala, Hunaid B; Luebke, David R

2012-12-05

Water interactions in 1-ethyl-3-methylimidazolium acetate ([emim][CH(3)COO]) were studied utilizing classical and ab initio simulation methods. The self-diffusivities for water and the ionic liquid (IL) were studied experimentally using pulse field gradient NMR spectroscopy and correlated with computational results. Water forms hydrogen bonding networks with the ionic liquid, and depending on the concentration of water, there are profound effects on the self-diffusivities of the various species. Both simulation and experiments show that the self-diffusivities for species in the water-[emim][CH(3)COO] system exhibit minima at 40-50 mol% water. Water interaction with the [CH(3)COO](-) anion predominates over the water-water and water-cation interactions at most water concentrations. Simulations further indicate that decreasing water-[CH(3)COO](-) interaction will increase the IL and water self-diffusivities. Self-diffusivities in the water-IL systems are dependent upon the cation in a complex way. Water interactions with [P(4444)][CH(3)COO] are reduced compared to [emim][CH(3)COO]. The [P(4444)](+) cation is bulkier than the [emim](+) cation and has a smaller self-diffusivity, but when water was introduced to [P(4444)] [CH(3)COO], the water-[CH(3)COO](-) hydrogen bonding network in the [P(4444)][CH(3)COO] was much smaller than the one observed in [emim][CH(3)COO].

The Role of Dopant Ions on Charge Injection and Transport in Electrochemically Doped Quantum Dot Films.

PubMed

Gudjonsdottir, Solrun; van der Stam, Ward; Kirkwood, Nicholas; Evers, Wiel H; Houtepen, Arjan J

2018-05-16

Control over the charge density is very important for implementation of colloidal semiconductor nanocrystals into various optoelectronic applications. A promising approach to dope nanocrystal assemblies is charge injection by electrochemistry, in which the charge compensating electrolyte ions can be regarded as external dopant ions. To gain insight into the doping mechanism and the role of the external dopant ions, we investigate charge injection in ZnO nanocrystal assemblies for a large series of charge compensating electrolyte ions with spectroelectrochemical and electrochemical transistor measurements. We show that charge injection is limited by the diffusion of cations in the nanocrystal films as their diffusion coefficient are found to be ∼7 orders of magnitude lower than those of electrons. We further show that the rate of charge injection depends strongly on the cation size and cation concentration. Strikingly, the onset of electron injection varies up to 0.4 V, depending on the size of the electrolyte cation. For the small ions Li + and Na + the onset is at significantly less negative potentials. For larger ions (K + , quaternary ammonium ions) the onset is always at the same, more negative potential, suggesting that intercalation may take place for Li + and Na + . Finally, we show that the nature of the charge compensating cation does not affect the source-drain electronic conductivity and mobility, indicating that shallow donor levels from intercalating ions fully hybridize with the quantum confined energy levels and that the reorganization energy due to intercalating ions does not strongly affect electron transport in these nanocrystal assemblies.

The Role of Dopant Ions on Charge Injection and Transport in Electrochemically Doped Quantum Dot Films

PubMed Central

2018-01-01

Control over the charge density is very important for implementation of colloidal semiconductor nanocrystals into various optoelectronic applications. A promising approach to dope nanocrystal assemblies is charge injection by electrochemistry, in which the charge compensating electrolyte ions can be regarded as external dopant ions. To gain insight into the doping mechanism and the role of the external dopant ions, we investigate charge injection in ZnO nanocrystal assemblies for a large series of charge compensating electrolyte ions with spectroelectrochemical and electrochemical transistor measurements. We show that charge injection is limited by the diffusion of cations in the nanocrystal films as their diffusion coefficient are found to be ∼7 orders of magnitude lower than those of electrons. We further show that the rate of charge injection depends strongly on the cation size and cation concentration. Strikingly, the onset of electron injection varies up to 0.4 V, depending on the size of the electrolyte cation. For the small ions Li+ and Na+ the onset is at significantly less negative potentials. For larger ions (K+, quaternary ammonium ions) the onset is always at the same, more negative potential, suggesting that intercalation may take place for Li+ and Na+. Finally, we show that the nature of the charge compensating cation does not affect the source-drain electronic conductivity and mobility, indicating that shallow donor levels from intercalating ions fully hybridize with the quantum confined energy levels and that the reorganization energy due to intercalating ions does not strongly affect electron transport in these nanocrystal assemblies. PMID:29718666

The Fe2(+)-Mg interdiffusion in orthopyroxene: Constraints from cation ordering and structural data and implications for cooling rates of meteorites

NASA Technical Reports Server (NTRS)

Ganguly, J.; Tazzoli, V.

1993-01-01

Orthopyroxene crystals in a number of meteorites exhibit compositional zoning of Fe and Mg, which provide important constraint on their cooling rates. However, attempts to model cooling rate of these crystals from Fe-Mg zoning profiles suffer from the lack of any measured or theoretically well constrained Fe-Mg interdiffusion data in OP(x) It has been assumed that Fe-Mg interdiffusion in OP(x) only slightly slower than that in olivine. The purpose of this paper is to (1) calculate the Fe-Mg fractionation, and (2) provide analytical formulation relating cooling rate to the length of the diffusion zone across the interface of the overgrowth of a mineral on itself with application to Mg diffusion profile across OP(x) growth on OP(x) in certain mesosiderites.

The influence of aliovalent impurities on the oxidation kinetics of nickel at high temperatures

NASA Astrophysics Data System (ADS)

Mrowec, S.; Grzesik, Z.; Rajchel, B.; Gil, A.; Dabek, J.

2005-01-01

The influence of chromium and sodium on the nickel oxidation kinetics has been studied as a function of temperature (1373-1673 K) and oxygen activity (10-105 Pa O2), using microthermogravimetric techniques. It has been shown that the oxidation of Ni-Cr and Ni-Na alloys, like that of pure nickel, follows strictly the parabolic rate law being thus diffusion controlled. In agreement with the defect model of Ni1-yO, it has been found that the oxidation rate of the Ni-Cr alloy is higher than that of pure nickel, the reaction rate is pressure independent and the activation energy of this process is lower. This implies that the concentration of double ionized cation vacancies in a Ni1-yO-Cr2O3 solid solution is fixed on a constant level by trivalent chromium ions, substitutionally incorporated into the cation sublattice of this oxide. In the case of the Ni-Na alloy, on the other hand, the oxidation rate is lower than that of pure nickel, the activation energy is higher and the oxidation rate increases more rapidly with oxygen pressure. These results can again be explained in terms of the doping effect, by assuming that univalent sodium ions dissolve substitutionally in the cation sublattice of nickel oxide.

An unusual slowdown of fast diffusion in a room temperature

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

Chathoth,; Mamontov, Eugene; Fulvio, Pasquale F

2013-01-01

Using quasielastic neutron scattering in the temperature range from 290 to 350 K, we show that the diffusive motions in a room temperature ionic liquid [H2NC(dma)2][BETI] become faster for a fraction of cations when the liquid is confined in a mesoporous carbon. This applies to both the localized and long-range translational diffusive motions of the highly mobile cations, although the former exhibit an unusual trend of slowing-down as the temperature is increased, until the localized diffusivity is reduced to the bulk ionic liquid value at a temperature of 350 K.

Electrically facilitated molecular transport. Analysis of the relative contributions of diffusion, migration, and electroosmosis to solute transport in an ion-exchange membrane.

PubMed

Bath, B D; White, H S; Scott, E R

2000-02-01

Electrically facilitated molecular transport in an ion-exchange membrane (Nafion, 1100 equiv wt) has been studied using a scanning electrochemical microscope. The transport rates of ferrocenylmethyltrimethylammonium (a cation), acetaminophen (a neutral molecule), and ascorbate (an anion) through approximately 120-micron-thick membranes were measured as a function of the iontophoretic current passed across the membrane (-1.0 to +1.0 A/cm2). Transport rates were analyzed by employing the Nernst-Planck equation, modified to account for electric field-driven convective transport. Excellent agreement between experimental and theoretical values of the molecular flux was obtained using a single fitting parameter for each molecule (electroosmotic drag coefficient). The electroosmotic velocity of the neutral molecule, acetaminophen, was shown to be a factor of approximately 500 larger than that of the cation ferrocenylmethyltrimethylammonium, a consequence of the electrostatic interaction of the cation with the negatively charged pore walls of the ion-exchange membrane. Electroosmotic transport of ascorbate occurred at a negligible rate due to repulsion of the anion by the cation-selective membrane. These results suggest that electroosmotic velocities of solute molecules are determined by specific chemical interactions of the permeant and membrane and may be very different from the average solution velocity. The efficiency of electroosmotic transport was also shown to be a function of the membrane thickness, in addition to membrane/solute interactions.

Ion transport with charge-protected and non-charge-protected cations using the compensated Arrhenius formalism. Part 2. Relationship between ionic conductivity and diffusion.

PubMed

Petrowsky, Matt; Fleshman, Allison; Bopege, Dharshani N; Frech, Roger

2012-08-09

Temperature-dependent ionic conductivities and cation/anion self-diffusion coefficients are measured for four electrolyte families: TbaTf-linear primary alcohols, LiTf-linear primary alcohols, TbaTf-n-alkyl acetates, and LiTf-n-alkyl acetates. The Nernst-Einstein equation does not adequately describe the data. Instead, the compensated Arrhenius formalism is applied to both conductivity and diffusion data. General trends based on temperature and alkyl chain length are observed when conductivity is plotted against cation or anion diffusion coefficient, but there is no clear pattern to the data. However, plotting conductivity exponential prefactors against those for diffusion results in four distinct curves, one each for the alcohol and acetate families described above. Furthermore, the TbaTf-alcohol and TbaTf-acetate data are "in line" with each other. The conductivity prefactors for the LiTf-alcohol data are smaller than those for the TbaTf data. The LiTf-acetate data have the lowest conductivity prefactors. This trend in prefactors mirrors the observed trend in degree of ionic association for these electrolytes.

Kinetic Monte Carlo Investigation of the Effects of Vacancy Pairing on Oxygen Diffusivity in Yttria-Stabilized Zirconia

NASA Technical Reports Server (NTRS)

Good, Brian S.

2011-01-01

Yttria-stabilized zirconia s high oxygen diffusivity and corresponding high ionic conductivity, and its structural stability over a broad range of temperatures, have made the material of interest for use in a number of applications, for example, as solid electrolytes in fuel cells. At low concentrations, the stabilizing yttria also serves to increase the oxygen diffusivity through the presence of corresponding oxygen vacancies, needed to maintain charge neutrality. At higher yttria concentration, however, diffusivity is impeded by the larger number of relatively high energy migration barriers associated with yttrium cations. In addition, there is evidence that oxygen vacancies preferentially occupy nearest-neighbor sites around either dopant or Zr cations, further affecting vacancy diffusion. We present the results of ab initio calculations that indicate that it is energetically favorable for oxygen vacancies to occupy nearest-neighbor sites adjacent to Y ions, and that the presence of vacancies near either species of cation lowers the migration barriers. Kinetic Monte Carlo results from simulations incorporating this effect are presented and compared with results from simulations in which the effect is not present.

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

PubMed

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

2016-04-28

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

Energetic and dynamic analysis of transport of Na + and K + through a cyclic peptide nanotube in water and in lipid bilayers

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

Song, Yeonho; Lee, Ji Hye; Hwang, Hoon

Potential of mean force (PMF) profiles and position-dependent diffusion coefficients of Na + and K + are calculated to elucidate the translocation of ions through a cyclic peptide nanotube, composed of 8 × cyclo[-(D-Leu-Trp) 4-] rings, in water and in hydrated DMPC bilayers. The PMF profiles and PMF decomposition analysis for the monovalent cations show that favorable interactions of the cations with the CPN as well as the lipid bilayer and dehydration free energy penalties are two major competing factors which determine the free energy surface for ion transport through CPNs both in water and lipid bilayers, and that themore » selectivity of CPNs to cations mainly arises from favorable interaction energies of cations with CPNs and lipid bilayers that are more dominant than the dehydration penalties. Calculations of the position-dependent diffusion coefficients and dynamic friction kernels of the cations indicate that the dehydration process along with the molecular rearrangements occurring outside the channel and the coupling of the ion motions with the chain-structured water movements inside the channel lead to decrease of the diffusion coefficients far away from the channel entrance and also reduced coefficients inside the channel. Here the PMF and diffusivity profiles for Na + and K + reveal that the energetics of ion transport through the CPN are governed by global interactions of ions with all the components in the system while the diffusivity of ions through the channel is mostly determined by local interactions of ions with the confined water molecules inside the channel. Comparison of Na + and K + ion distributions based on overdamped Brownian dynamics simulations based on the PMF and diffusivity profiles with the corresponding results from molecular dynamics shows good agreement, indicating accuracy of the Bayesian inference method for determining diffusion coefficients in this application. In addition this work shows that position-dependent diffusion coefficients of ions are required to explain the dynamics and conductance of ions through the CPN properly.« less

Energetic and dynamic analysis of transport of Na + and K + through a cyclic peptide nanotube in water and in lipid bilayers

DOE PAGES

Song, Yeonho; Lee, Ji Hye; Hwang, Hoon; ...

2016-11-04

Potential of mean force (PMF) profiles and position-dependent diffusion coefficients of Na + and K + are calculated to elucidate the translocation of ions through a cyclic peptide nanotube, composed of 8 × cyclo[-(D-Leu-Trp) 4-] rings, in water and in hydrated DMPC bilayers. The PMF profiles and PMF decomposition analysis for the monovalent cations show that favorable interactions of the cations with the CPN as well as the lipid bilayer and dehydration free energy penalties are two major competing factors which determine the free energy surface for ion transport through CPNs both in water and lipid bilayers, and that themore » selectivity of CPNs to cations mainly arises from favorable interaction energies of cations with CPNs and lipid bilayers that are more dominant than the dehydration penalties. Calculations of the position-dependent diffusion coefficients and dynamic friction kernels of the cations indicate that the dehydration process along with the molecular rearrangements occurring outside the channel and the coupling of the ion motions with the chain-structured water movements inside the channel lead to decrease of the diffusion coefficients far away from the channel entrance and also reduced coefficients inside the channel. Here the PMF and diffusivity profiles for Na + and K + reveal that the energetics of ion transport through the CPN are governed by global interactions of ions with all the components in the system while the diffusivity of ions through the channel is mostly determined by local interactions of ions with the confined water molecules inside the channel. Comparison of Na + and K + ion distributions based on overdamped Brownian dynamics simulations based on the PMF and diffusivity profiles with the corresponding results from molecular dynamics shows good agreement, indicating accuracy of the Bayesian inference method for determining diffusion coefficients in this application. In addition this work shows that position-dependent diffusion coefficients of ions are required to explain the dynamics and conductance of ions through the CPN properly.« less

[PAH Cations as Viable Carriers of DIBs

NASA Technical Reports Server (NTRS)

Snow, Ted

1998-01-01

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

Trace element diffusion and kinetic fractionation in wet rhyolitic melt

NASA Astrophysics Data System (ADS)

Holycross, Megan E.; Watson, E. Bruce

2018-07-01

Piston-cylinder experiments were run to determine the chemical diffusivities of 21 trace elements (Sc, V, Y, Zr, Nb, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Hf, Th and U) in hydrous rhyolitic melts at 1 GPa pressure and temperatures from 850 to 1250 °C. Diffusion couple glasses were doped with trace elements in low concentrations to characterize the diffusivities of all cations in a single experiment. Laser ablation ICP-MS was used to evaluate the trace element concentration gradients that developed in the silicate glasses. All calculated diffusion coefficients correspond to the temperature dependence D = D0exp(-Ea/RT). Rhyolite liquids contained either ∼4.1 wt% or ∼6.2 wt% dissolved H2O; separate Arrhenius relationships are produced for each melt composition. Trace element diffusivities in the melt with 6.2 wt% H2O are roughly two times higher than those in the less hydrous melt. Calculated trace element diffusion coefficients cover nearly two orders of magnitude at a given temperature. The high field strength elements are the slowest diffusers, followed by the transition metals and heavy rare earth elements. The light rare earth elements have the fastest diffusion rates in hydrous rhyolitic melt. The measured diffusion coefficients range down to values sufficiently low to preclude diffusive homogenization over geochemically realistic time scales in some cases. The substantial differences in the diffusivities of individual cations may result in fractionated trace element signatures in rhyolite melt pockets. A simple model is used to explore the potential for kinetic fractionation of REE during growth of an apatite crystal in a diffusive boundary layer locally saturated in P2O5. The faster-diffusing light REE are more efficiently transported away from the crystal interface than the slower-moving heavy REE. Diffusion effects will enrich the melt boundary layer in slow-moving HREE relative to the faster LREE. The kinetic fractionation of REE in the melt growth medium will result in a precipitated apatite crystal with a disequilibrium trace element composition.

Insights into gelation kinetics and gel front migration in cation-induced polysaccharide hydrogels by viscoelastic and turbidity measurements: Effect of the nature of divalent cations.

PubMed

Huynh, Uyen T D; Chambin, Odile; du Poset, Aline Maire; Assifaoui, Ali

2018-06-15

Polysaccharide-based hydrogels were prepared by the diffusion of various divalent cations (X 2+ ) into the polygalacturonate (polyGal) solution through a dialysis membrane. The diffusion of various divalent cations (Mg 2+ , Ca 2+ , Zn 2+ and Ba 2+ ) was investigated. The polyGal gel growth was studied as a function of the initial cation concentration by both viscoelastic and turbidity measurements. We have demonstrated for the first time that the determination of the spatiotemporal variation of turbidity during the gelation process allowed to study the gel front migration. For Ca-polyGal, Zn-polyGal and Ba-polyGal, the gel front migration was characterized by the presence of a peak at the sol/gel interface. This peak was not observed in the case of Mg-polyGal where the gel was not formed. The apparent diffusion coefficient of the gel front (D app ) which was calculated from the evolution of this peak increased when the initial cation concentration was increased. Moreover, we have suggested a gelation mechanism based on the presence of a threshold molar ratio R* (=[X 2+ ]/[Galacturonic unit]) in which some point-like crosslinks are precursors of the formation of dimers and multimers inducing the contraction of the gel and thus the formation of the gel front. Copyright © 2018 Elsevier Ltd. All rights reserved.

Wavy membranes and the growth rate of a planar chemical garden: Enhanced diffusion and bioenergetics.

PubMed

Ding, Yang; Batista, Bruno; Steinbock, Oliver; Cartwright, Julyan H E; Cardoso, Silvana S S

2016-08-16

To model ion transport across protocell membranes in Hadean hydrothermal vents, we consider both theoretically and experimentally the planar growth of a precipitate membrane formed at the interface between two parallel fluid streams in a 2D microfluidic reactor. The growth rate of the precipitate is found to be proportional to the square root of time, which is characteristic of diffusive transport. However, the dependence of the growth rate on the concentrations of hydroxide and metal ions is approximately linear and quadratic, respectively. We show that such a difference in ionic transport dynamics arises from the enhanced transport of metal ions across a thin gel layer present at the surface of the precipitate. The fluctuations in transverse velocity in this wavy porous gel layer allow an enhanced transport of the cation, so that the effective diffusivity is about one order of magnitude higher than that expected from molecular diffusion alone. Our theoretical predictions are in excellent agreement with our laboratory measurements of the growth of a manganese hydroxide membrane in a microfluidic channel, and this enhanced transport is thought to have been needed to account for the bioenergetics of the first single-celled organisms.

Cationic Contrast Agent Diffusion Differs Between Cartilage and Meniscus.

PubMed

Honkanen, Juuso T J; Turunen, Mikael J; Freedman, Jonathan D; Saarakkala, Simo; Grinstaff, Mark W; Ylärinne, Janne H; Jurvelin, Jukka S; Töyräs, Juha

2016-10-01

Contrast enhanced computed tomography (CECT) is a non-destructive imaging technique used for the assessment of composition and structure of articular cartilage and meniscus. Due to structural and compositional differences between these tissues, diffusion and distribution of contrast agents may differ in cartilage and meniscus. The aim of this study is to determine the diffusion kinematics of a novel iodine based cationic contrast agent (CA(2+)) in cartilage and meniscus. Cylindrical cartilage and meniscus samples (d = 6 mm, h ≈ 2 mm) were harvested from healthy bovine knee joints (n = 10), immersed in isotonic cationic contrast agent (20 mgI/mL), and imaged using a micro-CT scanner at 26 time points up to 48 h. Subsequently, normalized X-ray attenuation and contrast agent diffusion flux, as well as water, collagen and proteoglycan (PG) contents in the tissues were determined. The contrast agent distributions within cartilage and meniscus were different. In addition, the normalized attenuation and diffusion flux were higher (p < 0.05) in cartilage. Based on these results, diffusion kinematics vary between cartilage and meniscus. These tissue specific variations can affect the interpretation of CECT images and should be considered when cartilage and meniscus are assessed simultaneously.

Tunnel Structured α-MnO 2 with Different Tunnel Cations (H + , K + , Ag + ) as Cathode Materials in Rechargeable Lithium Batteries: The Role of Tunnel Cation on Electrochemistry

DOE PAGES

Poyraz, Altug S.; Huang, Jianping; Cheng, Shaobo; ...

2017-07-12

α-MnO 2 type manganese dioxide is an interesting prospective cathode material for reversible lithium insertion owing to its cation accessible tunnels (0.46nm x 0.46nm), high voltage, and low cost. The tunneled structure is synthetically formed by the assistance of cations acting as structure directing agents where the cations may remain in the tunnel. The electrochemistry of this family of materials is strongly dependent on the morphological and physicochemical (i.e. surface area, crystallite size, and average manganese oxidation state) properties as well as tunnel occupancy. For this work, we prepared a set of materials Mn 8O 16·0.81H 2O, K 0.81Mn 8Omore » 16·0.78H 2O and Ag 1.33Mn 8O 16·0.95H 2O with similar nanorod morphology, crystallite size, surface area, and tunnel water content. This set of samples allowed us to investigate the role of tunnel cations in the electrochemistry of α-MnO 2 type manganese dioxide in a lithium based environment while minimizing the effects of the other parameters. The electrochemistry was evaluated using cyclic voltammetry, galvanostatic cycling, rate capability, and galvanostatic intermittent titration type testing. Mn 8O 16·0.81H 2O showed higher loaded voltages, improved capacity retention, and higher specific energy relative to K 0.81Mn 8O 16·0.78H 2O and Ag 1.33Mn 8O 16·0.95H 2O. After 100 cycles, Mn 8O 16·0.81H 2O delivered ~200% more capacity than Ag 1.33Mn 8O 16·0.95H 2O (64 vs. 129 mAh/g) and ~35% more capacity than K 0.81Mn 8O 16·0.78H 2O (85 vs. 129 mAh/g). Mn 8O 16·0.81H 2O also showed higher effective lithium diffusion coefficients (DLi+) and higher rate capability compared to K 0.81Mn 8O 16·0.78H 2O and Ag 1.33Mn 8O 16·0.95H 2O suggesting faster Li+ ion diffusion in the absence of large metal tunnel cations.« less

Tunnel Structured α-MnO 2 with Different Tunnel Cations (H + , K + , Ag + ) as Cathode Materials in Rechargeable Lithium Batteries: The Role of Tunnel Cation on Electrochemistry

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

Poyraz, Altug S.; Huang, Jianping; Cheng, Shaobo

α-MnO 2 type manganese dioxide is an interesting prospective cathode material for reversible lithium insertion owing to its cation accessible tunnels (0.46nm x 0.46nm), high voltage, and low cost. The tunneled structure is synthetically formed by the assistance of cations acting as structure directing agents where the cations may remain in the tunnel. The electrochemistry of this family of materials is strongly dependent on the morphological and physicochemical (i.e. surface area, crystallite size, and average manganese oxidation state) properties as well as tunnel occupancy. For this work, we prepared a set of materials Mn 8O 16·0.81H 2O, K 0.81Mn 8Omore » 16·0.78H 2O and Ag 1.33Mn 8O 16·0.95H 2O with similar nanorod morphology, crystallite size, surface area, and tunnel water content. This set of samples allowed us to investigate the role of tunnel cations in the electrochemistry of α-MnO 2 type manganese dioxide in a lithium based environment while minimizing the effects of the other parameters. The electrochemistry was evaluated using cyclic voltammetry, galvanostatic cycling, rate capability, and galvanostatic intermittent titration type testing. Mn 8O 16·0.81H 2O showed higher loaded voltages, improved capacity retention, and higher specific energy relative to K 0.81Mn 8O 16·0.78H 2O and Ag 1.33Mn 8O 16·0.95H 2O. After 100 cycles, Mn 8O 16·0.81H 2O delivered ~200% more capacity than Ag 1.33Mn 8O 16·0.95H 2O (64 vs. 129 mAh/g) and ~35% more capacity than K 0.81Mn 8O 16·0.78H 2O (85 vs. 129 mAh/g). Mn 8O 16·0.81H 2O also showed higher effective lithium diffusion coefficients (DLi+) and higher rate capability compared to K 0.81Mn 8O 16·0.78H 2O and Ag 1.33Mn 8O 16·0.95H 2O suggesting faster Li+ ion diffusion in the absence of large metal tunnel cations.« less

Elemental and cooperative diffusion in a liquid, supercooled liquid and glass resolved

NASA Astrophysics Data System (ADS)

Cassar, Daniel R.; Lancelotti, Ricardo F.; Nuernberg, Rafael; Nascimento, Marcio L. F.; Rodrigues, Alisson M.; Diz, Luiza T.; Zanotto, Edgar D.

2017-07-01

The diffusion mechanisms controlling viscous flow, structural relaxation, liquid-liquid phase separation, crystal nucleation, and crystal growth in multicomponent glass-forming liquids are of great interest and relevance in physics, chemistry, materials, and glass science. However, the diffusing entities that control each of these important dynamic processes are still unknown. The main objective of this work is to shed some light on this mystery, advancing the knowledge on this phenomenon. For that matter, we measured the crystal growth rates, the viscosity, and lead diffusivities in PbSiO3 liquid and glass in a wide temperature range. We compared our measured values with published data covering 16 orders of magnitude. We suggest that above a certain temperature range Td (1.2Tg-1.3Tg), crystal growth and viscous flow are controlled by the diffusion of silicon and lead. Below this temperature, crystal growth and viscous flow are more sluggish than the diffusion of silicon and lead. Therefore, Td marks the temperature where decoupling between the (measured) cationic diffusivity and the effective diffusivities calculated from viscosity and crystal growth rates occurs. We reasonably propose that the nature or size of the diffusional entities controlling viscous flow and crystal growth below Td is quite different; the slowest is the one controlling viscous flow, but both processes require cooperative movements of some larger structural units rather than jumps of only one or a few isolated atoms.

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

NASA Astrophysics Data System (ADS)

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

2014-09-01

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

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

DOE PAGES

Uberuaga, Blas Pedro; Pilania, Ghanshyam

2015-07-08

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

ZitB (YbgR), a Member of the Cation Diffusion Facilitator Family, Is an Additional Zinc Transporter in Escherichia coli

PubMed Central

Grass, Gregor; Fan, Bin; Rosen, Barry P.; Franke, Sylvia; Nies, Dietrich H.; Rensing, Christopher

2001-01-01

The Escherichia coli zitB gene encodes a Zn(II) transporter belonging to the cation diffusion facilitator family. ZitB is specifically induced by zinc. ZitB expression on a plasmid rendered zntA-disrupted E. coli cells more resistant to zinc, and the cells exhibited reduced accumulation of 65Zn, suggesting ZitB-mediated efflux of zinc. PMID:11443104

Kinetic model for the short-term dissolution of a rhyolitic glass

USGS Publications Warehouse

White, A.F.; Claassen, H.C.

1980-01-01

Aqueous dissolution experiments with the vitric phase of a rhyolitic tuff were performed at 25??C and constant pH in the range 4.5-7.5. Results suggest interchange of aqueous hydrogen ions for cations situated both on the surface and within the glass. At time intervals from 24 to 900 hr., dissolution kinetics are controlled by ion transport to and from sites within the glass. Experimental data indicate that parabolic diffusion rate of a chemical species from the solid is a nonlinear function of its aqueous concentration. A numerical solution to Fick's second law is presented for diffusion of sodium, which relates it's aqueous concentration to it's concentration on glass surface, by a Freundlich adsorption isotherm. The pH influence on sodium diffusion in the model can be accounted for by use of a pH-dependent diffusion coefficient and a pH-independent adsorption isotherm. ?? 1980.

Cation dynamics in the pyridinium based ionic liquid 1-N-butylpyridinium bis((trifluoromethyl)sulfonyl) as seen by quasielastic neutron scattering.

PubMed

Embs, Jan P; Burankova, Tatsiana; Reichert, Elena; Hempelmann, Rolf

2012-11-08

Quasielastic neutron scattering (QENS) has been used to study the cation dynamics in the pyridinium based ionic liquid (IL) 1-N-butylpyridinium bis((trifluoromethyl)sulfonyl)imide (BuPy-Tf(2)N). This IL allows for a detailed investigation of the dynamics of the cations only, due to the huge incoherent scattering cross section of the cation (σ(inc)(cation) > σ(inc)(anion)). The measured spectra can be decomposed into two Lorentzian lines, indicative of two distinct dynamic processes. The slower of these two processes is diffusive in nature, whereas the faster one can be attributed to localized motions. The temperature dependence of the diffusion coefficient of the slow process follows an Arrhenius law, with an activation energy of E(A) = 14.8 ± 0.3 kJ/mol. Furthermore, we present here results from experiments with polarized neutrons. These experiments clearly show that the slower of the two observed processes is coherent, while the faster one is incoherent in nature.

Diffusion, sorption, and retardation processes of anions in bentonite and organo-bentonites for multibarrier systems

NASA Astrophysics Data System (ADS)

Schampera, Birgit; Dultz, Stefan

2013-04-01

The low permeability, high cation exchange capacity (CEC) and plasticity of bentonites favor their use in multibarrier systems of waste deposits [1]. Bentonites have a high CEC but their ability to sorb anions is very low. There is, however, need for retardation of anions and organic pollutants in many applications. Bentonites, modified with certain organic cations, have the capacity to sorb anions and non-polar organic compounds in addition to cations. Investigations on organically modified clays address a wide variety of applications including immobilization of pollutants in contaminated soils, waste water treatment and in situ placement for the protection of ground water [2]. Many experiments on anion and cation sorption of organo-clays were conducted in the batch mode which does not reflect solid-liquid ratios and material densities in barrier systems. Diffusion experiments on compacted clays allow the evaluation of transport processes and sorption of pollutants at conditions relevant for repositories. For organo-clays only few diffusion studies are published e.g. [3] measured the diffusion of tritium and [4] the diffusion of H2O in bentonite and organo-bentonites. The organic cation hexadecylpyridinium (HDPy) was added to Wyoming bentonite (MX-80) in amounts corresponding to 2-400 % of the CEC. The uptake of organic cations was determined by the C-content, XRD and IR-spectroscopy. Wettability was analyzed by the contact angle. Physical, chemical and mineralogical properties of clays were characterized. Diffusion experiments were carried out in situ in a cell attached to the ATR-unit of a FTIR-spectrometer. For H2O-diffusion the compacted organo-clays are saturated first with D2O, afterwards H2O is supplied to the surface at the top of the clay platelet. Anion-diffusion was conducted with NO3--solution instead of H2O only having characteristic IR band positions at 1350 cm-1. Three different concentrations (0.25M, 0.5M and 1M) were used. Additional batch experiments with NO3- will support the understanding of sorption behavior of the anions. All hydrophilic samples have a higher retardation capacity, indicated by diffusion coefficients of 2.44 x 10-11 m/s2 for original bentonite and ˜2.1 x 10-11m/s2 for hydrophilic organo-clays. For hydrophobic organo-clays the H2O diffusion can be higher and is increased at high bulk density (1-1.5 g/m3) up to 2.76 x 10-10m2/s. Experiments with NO3- at bulk density of 1.5 g/m3 reveal that the apparent diffusion coefficients of nitrate are with results up to 5.61 x 1012 m2/s distinctively lower than free diffusion of nitrate in pure water (6.46 x 1010 m2/s at experimental conditions) and nitrate diffusion in natural bentonite (2.63 x 1011 m2/s). The measurements allow the interpretation of the different sorption mechanisms, retardation capacity and diffusion behavior of the analyzed clays at different anion concentrations. Ongoing molecular dynamic simulations will contribute understanding of diffusion processes in organo-clays including the conditions at the interface of the clay minerals and in solution. References: [1] Shackelford, C.D., Moore S.M. (2013) Fickian diffusion of radionuclides for engineered containment barriers: Diffusion coefficients, porosities, and complicating issues. Engineering Geology, 152, 133-147. [2] Rytwo, G., Nir, S., Shuali, U. (2012) Clay and water treatment. Applied Clay Science, 67-68, 117-118. [3] Lorenzetti, R.L., Bartelt-Hunt, S.L., Burns, S.E., Smith, J.A. (2005) Hydraulic conductivities and effective diffusion coefficients of geosynthetic clay liners with organobentonite amendments. Geotextiles and Geomembranes, 23, 385-400. [4] Schampera, B., Dultz, S. (2011) H2O self-diffusion in compacted clays as influenced by surface charge and wettability - obstruction effects of bound H2O layers. Clay and Clay Minerals,59, 42-57.

Effects of cation contaminants in conductive TiO2 ceramics

NASA Astrophysics Data System (ADS)

Yan, M. F.; Rhodes, W. W.

1982-12-01

Ten cation contaminants, namely Al, Ga, Co, Fe, Mg, Zn, Zr, Ca, Sr, and Ba were investigated for their effects on the electrical properties, microstructures, and discoloration of conductive TiO2 ceramics. It was found that Al, Ga, Co, Fe, and Mg cause discoloration and increase the electrical resistivity by a factor of 104 to 106 in Nb-doped TiO2 ceramics. The other dopants do not introduce such changes in TiO2. The electrical properties, microstructures, and discoloration were measured in specimens of AlxNb0.007Ti0.993-xO2 with 0≤x≤0.01. When the Al content exceeds a critical value, ranging from 0.48% at 1400 °C to 0.25% at 1200 °C, the electrical resistivities and grain size increase rapidly, and the specimen is discolored from the original black to an ivory white color. Color boundary migration induced by Al diffusion in Nb-doped TiO2 was quantitatively measured. From the kinetics of the boundary migration, the Al diffusivity (D) was calculated to be D=2.67 exp(-53.3 kcal/mole/RT) cm2/s in the temperature range of 1200 to 1400 °C. The rapid diffusion of the small cations, namely Al, Ga, Co, Fe, and Mg, results from an interstitial diffusion mechanism. However, other cations, having a radius larger than the interstitial channel (˜0.77 Å radius), cannot diffuse by this mechanism. Defect reactions are proposed to explain the increase in the electrical resistivity and microstructural changes due to Al diffusion. These defect reactions also show that the problem of acceptor contamination cannot be avoided by adding an excess quantity of donor dopant if the solubility of the donor is much less than that of the acceptor contaminant.

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

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

Tian, Lei; Shi, Zhenqing; Lu, Yang

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

On the role of humic acids' carboxyl groups in the binding of charged organic compounds.

PubMed

Smilek, Jiří; Sedláček, Petr; Kalina, Michal; Klučáková, Martina

2015-11-01

Interactions of humic acids (HAs) with two cationic dyes (methylene blue and rhodamine 6G) were studied using a unique combination of diffusion and partitioning studies in HAs, containing hydrogels and batch sorption experiments. In order to investigate the involvement of carboxyl groups of HAs in these interactions, all experiments were performed for both, the original lignite HAs and HAs with selectively methylated carboxyls. The results of the diffusion experiments confirm that the interactions between the solute and humic substances have a strong impact on the rate of diffusion process. Surprisingly, the effect is almost equally approved for original and methylated HAs. On the other hand, the results of batch sorption experiments show strong improvement of the sorption capacity (methylated HAs), which is explained by changed morphology of alkylated HAs. The comparison of the results of diffusion and adsorption experiments shows that the diffusion experiments simulate the transport of solutes in natural humics containing environment more reasonably. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

NASA Technical Reports Server (NTRS)

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

2002-01-01

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

Experimental characterization and modelization of ion exchange kinetics for a carboxylic resin in infinite solution volume conditions. Application to monovalent-trivalent cations exchange.

PubMed

Picart, Sébastien; Ramière, Isabelle; Mokhtari, Hamid; Jobelin, Isabelle

2010-09-02

This study is devoted to the characterization of ion exchange inside a microsphere of carboxylic resin. It aims at describing the kinetics of this exchange reaction which is known to be controlled by interdiffusion in the particle. The fractional attainment of equilibrium function of time depends on the concentration of the cations in the resin which can be modelized by the Nernst-Planck equation. A powerful approach for the numerical resolution of this equation is introduced in this paper. This modeling is based on the work of Helfferich but involves an implicit numerical scheme which reduces the computational cost. Knowing the diffusion coefficients of the cations in the resin and the radius of the spherical exchanger, the kinetics can be hence completely determined. When those diffusion parameters are missing, they can be deduced by fitting experimental data of fractional attainment of equilibrium. An efficient optimization tool coupled with the implicit resolution has been developed for this purpose. A monovalent/trivalent cation exchange had been experimentally characterized for a carboxylic resin. Diffusion coefficients and concentration profiles in the resin were then deduced through this new model.

The effect of various electrolyte cations on electrochemical performance of polypyrrole/RGO based supercapacitors.

PubMed

Zhu, Jianbo; Xu, Youlong; Wang, Jie; Lin, Jun; Sun, Xiaofei; Mao, Shengchun

2015-11-21

In this work, polypyrrole/graphene doped by p-toluenesulfonic is prepared as an active material for supercapacitors, and its capacitance performance is investigated in various aqueous electrolytes including HCl, LiCl, NaCl, and KCl with a concentration of 3 M, respectively. A rising trend of capacitance is observed according to the cationic mobility (Li(+) < Na(+) < K(+) < H(+)), which is due to its effect on the ionic conductivity, efficient ion/charge diffusion/exchange and relaxation time. On the other hand, long-term cycling stability is in the following order: KCl < NaCl < LiCl < HCl, corresponding to the decreasing tendency of cation size (K(+) > Na(+) > Li(+) > H(+)). The reason can be attributed to the fact that the insertion/de-insertion of large size cation brings a significant doping level decrease and an over-oxidation increase during the charging-discharging cycles. Hence, we not only obtain good capacitance performance (280.3 F g(-1) at 5 mV s(-1)), superior rate capability (225.8 F g(-1) at 500 mV s(-1)) and high cycling stability (92.0% capacitance retention after 10,000 cycles at 1 A g(-1)) by employing 3 M HCl as an electrolyte, but also reveal that the electrolyte cations have a significant effect on the supercapacitors' electrochemical performance.

Electronic spectra of astrophysically interesting cations

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

Maier, John P., E-mail: j.p.maier@unibas.ch; Rice, Corey A., E-mail: j.p.maier@unibas.ch; Mazzotti, Fabio J., E-mail: j.p.maier@unibas.ch

2015-01-22

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

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

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

Kofu, Maiko; Inamura, Yasuhiro; Miyazaki, Kyoko

2015-12-21

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

Real Time Quantification of Ultrafast Photoinduced Bimolecular Electron Transfer Rate: Direct Probing of the Transient Intermediate.

PubMed

Mukherjee, Puspal; Biswas, Somnath; Sen, Pratik

2015-08-27

Fluorescence quenching studies through steady-state and time-resolved measurements are inadequate to quantify the bimolecular electron transfer rate in bulk homogeneous solution due to constraints from diffusion. To nullify the effect of diffusion, direct evaluation of the rate of formation of a transient intermediate produced upon the electron transfer is essential. Methyl viologen, a well-known electron acceptor, produces a radical cation after accepting an electron, which has a characteristic strong and broad absorption band centered at 600 nm. Hence it is a good choice to evaluate the rate of photoinduced electron transfer reaction employing femtosecond broadband transient absorption spectroscopy. The time constant of the aforementioned process between pyrene and methyl viologen in methanol has been estimated to be 2.5 ± 0.4 ps using the same technique. The time constant for the backward reaction was found to be 14 ± 1 ps. These values did not change with variation of concentration of quencher, i.e., methyl viologen. Hence, we can infer that diffusion has no contribution in the estimation of rate constants. However, on changing the solvent from methanol to ethanol, the time constant of the electron transfer reaction has been found to increase and has accounted for the change in solvent reorganization energy.

Transport of Organic Compounds Through Porous Systems Containing Humic Acids.

PubMed

Smilek, Jiri; Sedlacek, Petr; Lastuvkova, Marcela; Kalina, Michal; Klucakova, Martina

2017-03-01

Soil pollution by the presence of different contaminants (e.g. heavy metal ions or pesticides) is one of the biggest problems worldwide. The positive affinity of natural humic acids towards these contaminants might contribute to the soil and ground water protection; therefore it is necessary to study the reactivity and barrier properties of humic acids. An original reactivity-mapping tool based on diffusion techniques designed to study the reactivity and barrier properties of polyelectrolytes was developed and tested on humic acids. The results of diffusion experiments demonstrate that the electrostatic interactions between humic acids functioning as a polyelectrolyte interpenetrated in a supporting hydrogel matrix (agarose) and cationic dye (methylene blue) as a model solute have a crucial impact on the rate of diffusion processes and on the barrier properties of hydrogels. The intensity of interactions was evaluated by fundamental diffusion parameters (effective diffusion coefficients and breakthrough time). The impact of modification of humic acids was also studied by means of diffusion experiments conducted on two types of standard humic acids (Leonardite 1S104H) and humic acids with selectively methylated carboxylic groups.

A model for self-diffusion of guanidinium-based ionic liquids: a molecular simulation study.

PubMed

Klähn, Marco; Seduraman, Abirami; Wu, Ping

2008-11-06

We propose a novel self-diffusion model for ionic liquids on an atomic level of detail. The model is derived from molecular dynamics simulations of guanidinium-based ionic liquids (GILs) as a model case. The simulations are based on an empirical molecular mechanical force field, which has been developed in our preceding work, and it relies on the charge distribution in the actual liquid. The simulated GILs consist of acyclic and cyclic cations that were paired with nitrate and perchlorate anions. Self-diffusion coefficients are calculated at different temperatures from which diffusive activation energies between 32-40 kJ/mol are derived. Vaporization enthalpies between 174-212 kJ/mol are calculated, and their strong connection with diffusive activation energies is demonstrated. An observed formation of cavities in GILs of up to 6.5% of the total volume does not facilitate self-diffusion. Instead, the diffusion of ions is found to be determined primarily by interactions with their immediate environment via electrostatic attraction between cation hydrogen and anion oxygen atoms. The calculated average time between single diffusive transitions varies between 58-107 ps and determines the speed of diffusion, in contrast to diffusive displacement distances, which were found to be similar in all simulated GILs. All simulations indicate that ions diffuse by using a brachiation type of movement: a diffusive transition is initiated by cleaving close contacts to a coordinated counterion, after which the ion diffuses only about 2 A until new close contacts are formed with another counterion in its vicinity. The proposed diffusion model links all calculated energetic and dynamic properties of GILs consistently and explains their molecular origin. The validity of the model is confirmed by providing an explanation for the variation of measured ratios of self-diffusion coefficients of cations and paired anions over a wide range of values, encompassing various ionic liquid classes as well as the simulated GILs. The proposed diffusion model facilitates the qualitative a priori prediction of the impact of ion modifications on the diffusive characteristics of new ionic liquids.

Molecular dynamic simulation of dicationic ionic liquids: effects of anions and alkyl chain length on liquid structure and diffusion.

PubMed

Yeganegi, Saeid; Soltanabadi, Azim; Farmanzadeh, Davood

2012-09-20

Structures and dynamics of nine geminal dicationic ionic liquids (DILs) Cn(mim)2X2, where n = 3, 6, and 9 and X = PF6(-), BF4(-), and Br(-), were studied by molecular dynamic simulations (J. Phys. Chem.B2004, 108, 2038-2047). A force field with a minor modification for C3(mim)2 × 2 was adopted for the simulations. Densities, detailed microscopic structures, mean-square displacements (MSD), and self-diffusivities for various ion pairs from MD simulations have been presented. The calculated densities for C9(mim)2X2 (X = Br(-) and BF4(-)) agreed well with the experimental values. The calculated RDFs show that anions are well organized around the imidazolium rings. The calculated RDFs indicate that, unlike the mono cationic ILs, the anions and cations in DILs distribute homogeneously. Enthalpies of vaporization were calculated and correlated with the structural features of DILs. The local structure of C9(mim)2X2 (X = Br, PF6) was examined by the spatial distribution function (SDF). The calculated SDFs show that similar trends were found by other groups for mono cationic ionic liquids (ILs). The highest probability densities are located around the imidazolium ring hydrogens. The calculated diffusion coefficients show that the ion diffusivities are 1 order of magnitude smaller than that of the mono cationic ionic liquids. The effects of alkyl chain length and anion type on the diffusion coefficient were also studied. The dynamics of the imidazolium rings and the alkyl chain in different time scales have also discussed. The calculated transference numbers show that the anions have the major role in carrying the electric current in a DIL.

Diffusion and Electric Mobility of Ions within Isolated Cuticles of Citrus aurantium 1

PubMed Central

Tyree, Melvin T.; Wescott, Charles R.; Tabor, Christopher A.

1991-01-01

We report a new method for measuring cation and anion permeability across cuticles of sour orange, Citrus aurantium, leaves. The method requires the measurement of two electrical parameters: the diffusion potential arising when the two sides of the cuticle are bathed in unequal concentrations of a Cl− salt; and the electrical conductance of the cuticle measured at a salt concentration equal to the average of that used in the diffusion-potential measurement. The permeabilities of H+, Li+, Na+, K+, and Cs+ ranged from 2 × 10−8 to 0.6 × 10−8 meters per second when cuticles were bathed in 2 moles per cubic meter Cl− salts. The permeability of Cl− was 3 × 10−9 meters per second. The permeability of Li+, Na+, and K+ was about five times less when measured in 500 moles per cubic meter Cl− salts. We also report an asymmetry in cuticle-conductance values depending on the magnitude and the direction of current flow. The asymmetry disappears at low current-pulse magnitude and increases linearly with the magnitude of the current pulse. This phenomenon is explained in terms of transport-number effects in a bilayer model of the cuticle. Conductance is not augmented by current carried by exchangeable cations in cuticles; conductance is rate limited by the outer waxy layer of the cuticle. PMID:16668382

Disorder-induced transition from grain boundary to bulk dominated ionic diffusion in pyrochlores

DOE PAGES

Perriot, Romain; Dholabhai, Pratik P.; Uberuaga, Blas P.

2017-05-04

In this paper, we use molecular dynamics simulations to investigate the role of grain boundaries (GBs) on ionic diffusion in pyrochlores, as a function of the GB type, chemistry of the compound, and level of cation disorder. We observe that the presence of GBs promotes oxygen transport in ordered and low-disordered systems, as the GBs are found to have a higher concentration of mobile carriers with higher mobilities than in the bulk. Thus, in ordered samples, the ionic diffusion is 2D, localized along the grain boundary. When cation disorder is introduced, bulk carriers begin to contribute to the overall diffusion,more » while the GB contribution is only slightly enhanced. In highly disordered samples, the diffusive behavior at the GBs is bulk-like, and the two contributions (bulk vs. GB) can no longer be distinguished. There is thus a transition from 2D/GB dominated oxygen diffusivity to 3D/bulk dominated diffusivity versus disorder in pyrochlores. Finally, these results provide new insights into the possibility of using internal interfaces to enhance ionic conductivity in nanostructured complex oxides.« less

Connecting the molecular scale to the continuum scale for diffusion processes in smectite-rich porous media.

PubMed

Bourg, Ian C; Sposito, Garrison

2010-03-15

In this paper, we address the manner in which the continuum-scale diffusive properties of smectite-rich porous media arise from their molecular- and pore-scale features. Our starting point is a successful model of the continuum-scale apparent diffusion coefficient for water tracers and cations, which decomposes it as a sum of pore-scale terms describing diffusion in macropore and interlayer "compartments." We then apply molecular dynamics (MD) simulations to determine molecular-scale diffusion coefficients D(interlayer) of water tracers and representative cations (Na(+), Cs(+), Sr(2+)) in Na-smectite interlayers. We find that a remarkably simple expression relates D(interlayer) to the pore-scale parameter δ(nanopore) ≤ 1, a constrictivity factor that accounts for the lower mobility in interlayers as compared to macropores: δ(nanopore) = D(interlayer)/D(0), where D(0) is the diffusion coefficient in bulk liquid water. Using this scaling expression, we can accurately predict the apparent diffusion coefficients of tracers H(2)0, Na(+), Sr(2+), and Cs(+) in compacted Na-smectite-rich materials.

Modification of molybdenum surface by low-energy oxygen implantation at room temperature

NASA Astrophysics Data System (ADS)

Kavre Piltaver, Ivna; Jelovica Badovinac, Ivana; Peter, Robert; Saric, Iva; Petravic, Mladen

2017-12-01

We have studied the initial stages of oxide formation on molybdenum surfaces under 1 keV O2+ ion bombardment at room temperature (RT), using x-ray photoelectron spectroscopy around Mo 3d or O 1s core-levels and the valence band photoemission. The results are compared with the oxidation mechanism of thermally oxidized Mo at RT. The thermal oxidation reveals the formation of a very thin MoO2 layer that prevents any further adsorption of oxygen at higher oxygen doses. Oxygen implantation is more efficient in creating thicker oxide films with the simultaneous formation of several oxide compounds. The oxidation rates of MoO2 and Mo2O5 follow the parabolic growth rate consistent with the mass transport driven by diffusion of either neutral or singly and doubly charged oxygen interstitials. The oxidation of MoO3, which occurs at a later oxidation stage, follows the logarithmic rate driven by the diffusion of cations in an electric field.

Effects of sorption competition on caesium diffusion through compacted argillaceous rock

NASA Astrophysics Data System (ADS)

Jakob, Andreas; Pfingsten, Wilfried; Van Loon, Luc

2009-05-01

We carried out a small-scale laboratory diffusion experiment on a disk-like sample of Opalinus clay from the Mont Terri underground laboratory (Switzerland) using 134Cs as tracer. A through-diffusion phase was followed by an out-diffusion phase where the tracer taken up by the sample was released again. Since the tracer concentration at both boundaries was monitored, careful mass-balance considerations were feasible. A first analysis of the experimental data was done in the frame of a single-species model accounting only for transport and non-linear sorption of caesium. The model could match the data of the through-diffusion phase, however only, when strongly reducing the sorption data based on batch sorption experiments. Yet, such a procedure was in strong contradiction with sorption measurements performed on dispersed and compacted systems. In addition, predictions concerning tracer out-diffusion and mass-balance considerations clearly revealed the shortcomings of this type of model. In a second attempt we applied a multi-species transport model where now the whole water chemistry and a sorption model for caesium were considered. First, the value for the diffusion coefficient was fixed to the best-fit value of the single-species model. But again, the sorption site densities had to be reduced strongly albeit the reduction factor was smaller. Only when fixing the sorption site densities to those values of the sorption model and letting the effective diffusion coefficient D e free for the adjustment, could through-diffusion data be reasonably well fitted and out-diffusion as well as mass-balances be predicted in a satisfying manner. The main results are: (1) The best-fit could be achieved with a value for D e of 1.8 × 10 -10 m 2 s -1 which is rather high but corroborated by results of a molecular modelling study. (2) If caesium arrives in the Opalinus clay sample potassium and sodium (calcium etc.) ions are released and caesium ions are sorbed. The released cations diffuse to lower concentration regions according to their individual concentration gradients. Since locally the cation concentration for potassium, (sodium and calcium) is increased, sorption of these cations is also locally enhanced, affecting in return the sorption behaviour of migrating caesium. Consequently, the sorption process of caesium in such diffusion experiments cannot be addressed by a non-linear isotherm formalism any longer. (3) A reasonable analysis of such single tracer diffusion experiments therefore requires the combined description of transport (diffusion) and sorption of many cations and the whole complex water chemistry of the system. Thus, single-species models can only be applied with care in the considered concentration ranges.

Rates and mechanisms of the atomic oxygen reaction with nickel at elevated temperatures

NASA Technical Reports Server (NTRS)

Christian, J. D.; Gilbreath, W. P.

1973-01-01

The oxidation of nickel by atomic oxygen at pressure from 1 to 45 N/sq m between 1050 and 1250 K was investigated. In these ranges, the oxidation was found to follow the parobolic rate law, viz., K sub p = 0.0000114 exp(-13410/T) g squared/cm4/sec for films of greater than 1 micron thickness and was pressure independent. The activation enthalpy for the oxidation reaction was 112 + or - 11 kj/mole (27 + or - 3 kcal/mole). Of a number of possible mechanisms and defect structures considered, it was shown that the most likely was a saturated surface defect model for atomic oxidation, based on reaction activation enthalpies, impurity effects, pressure independence, and magnitudes of rates. A model judged somewhat less likely was one having doubly ionized cationic defects rate controlling in both atomic and molecular oxygen. From comparisons of the appropriate processes, the following enthalpy values were derived: enthalpy of activation (Ni diffusion in Ni0) = 110 + or - 30 kj/mole and standard enthalpy change for reaction formation (doubly ionized cation vacancies in Ni0 from atomic oxygen)= -9 + or - 25 kj/mole.

Equilibrium and kinetic adsorption study of a cationic dye by a natural adsorbent--silkworm pupa.

PubMed

Noroozi, B; Sorial, G A; Bahrami, H; Arami, M

2007-01-02

In this work the use of silkworm pupa, which is the waste of silk spinning industries has been investigated as an adsorbent for the removal of C.I. Basic Blue 41. The amino acid nature of the pupa provided a reasonable capability for dye removal. Equilibrium adsorption isotherms and kinetics were investigated. The adsorption equilibrium data were analyzed by using various adsorption isotherm models and the results have shown that adsorption behavior of the dye could be described reasonably well by either Langmuir or Freundlich models. The characteristic parameters for each isotherm have been determined. The monolayer adsorption capacity was determined to be 555 mg/g. Kinetic studies indicated that the adsorption follows pseudo-second-order kinetics with a rate constant of 0.0434 and 0.0572 g/min mg for initial dye concentration of 200 mg/l at 20 and 40 degrees C, respectively. Kinetic studies showed that film diffusion and intra-particle diffusion were simultaneously operating during the adsorption process. The rate constant for intra-particle diffusion was estimated to be 1.985 mg/g min(0.5).

A first-principles and experimental study of helium diffusion in periclase MgO

NASA Astrophysics Data System (ADS)

Song, Zhewen; Wu, Henry; Shu, Shipeng; Krawczynski, Mike; Van Orman, James; Cherniak, Daniele J.; Bruce Watson, E.; Mukhopadhyay, Sujoy; Morgan, Dane

2018-02-01

The distribution of He isotopes is used to trace heterogeneities in the Earth's mantle, and is particularly useful for constraining the length scale of heterogeneity due to the generally rapid diffusivity of helium. However, such an analysis is challenging because He diffusivities are largely unknown in lower mantle phases, which can influence the He profiles in regions that cycle through the lower mantle. With this motivation, we have used first-principles simulations based on density functional theory to study He diffusion in MgO, an important lower mantle phase. We first studied the case of interstitial helium diffusion in perfect MgO and found a migration barrier of 0.73 eV at zero pressure. Then we used the kinetic Monte Carlo method to study the case of substitutional He diffusion in MgO, where we assumed that He diffuses on the cation sublattice through cation vacancies. We also performed experiments on He diffusion at atmospheric pressure using ion implantation and nuclear reaction analysis in both as-received and Ga-doped samples. A comparison between the experimental and simulation results are shown. This work provides a foundation for further studies at high-pressure.

Diffusion controlled initial recombination

NASA Astrophysics Data System (ADS)

Christen, T.; Büttiker, M.

1998-08-01

This work addresses nucleation rates in systems with strong initial recombination. Initial (or ``geminate'') recombination is a process where a dissociated structure (anion, vortex, kink, etc.) recombines with its twin brother (cation, antivortex, antikink) generated in the same nucleation event. Initial recombination is important if there is an asymptotically vanishing interaction force instead of a generic saddle-type activation barrier. At low temperatures, initial recombination strongly dominates homogeneous recombination. In a first part, we discuss the effect in one-, two-, and three-dimensional diffusion controlled systems with spherical symmetry. Since there is no well-defined saddle, we introduce a threshold which is to some extent arbitrary but which is restricted by physically reasonable conditions. We show that the dependence of the nucleation rate on the specific choice of this threshold is strongest for one-dimensional systems and decreases in higher dimensions. We also discuss the influence of a weak driving force, and show that the transport current is directly determined by the imbalance of the activation rate in the direction of the field and the rate against this direction. In a second part, we apply the results to the overdamped sine-Gordon system at equilibrium. It turns out that diffusive initial recombination is the essential mechanism which governs the equilibrium kink nucleation rate. We emphasize analogies between the single particle problem with initial recombination and the multidimensional kink-antikink nucleation problem.

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

Perriot, Romain; Dholabhai, Pratik P.; Uberuaga, Blas P.

In this paper, we use molecular dynamics simulations to investigate the role of grain boundaries (GBs) on ionic diffusion in pyrochlores, as a function of the GB type, chemistry of the compound, and level of cation disorder. We observe that the presence of GBs promotes oxygen transport in ordered and low-disordered systems, as the GBs are found to have a higher concentration of mobile carriers with higher mobilities than in the bulk. Thus, in ordered samples, the ionic diffusion is 2D, localized along the grain boundary. When cation disorder is introduced, bulk carriers begin to contribute to the overall diffusion,more » while the GB contribution is only slightly enhanced. In highly disordered samples, the diffusive behavior at the GBs is bulk-like, and the two contributions (bulk vs. GB) can no longer be distinguished. There is thus a transition from 2D/GB dominated oxygen diffusivity to 3D/bulk dominated diffusivity versus disorder in pyrochlores. Finally, these results provide new insights into the possibility of using internal interfaces to enhance ionic conductivity in nanostructured complex oxides.« less

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

Jain, Richa Naja, E-mail: ltprichanaja@gmail.com; Chakraborty, Brahmananda; Ramaniah, Lavanya M.

In this work our main objective is to compute Dynamical correlations, Onsager coefficients and Maxwell-Stefan (MS) diffusivities for molten salt LiF-KF mixture at various thermodynamic states through Green–Kubo formalism for the first time. The equilibrium molecular dynamics (MD) simulations were performed using BHM potential for LiF–KF mixture. The velocity autocorrelations functions involving Li ions reflect the endurance of cage dynamics or backscattering with temperature. The magnitude of Onsager coefficients for all pairs increases with increase in temperature. Interestingly most of the Onsager coefficients has almost maximum magnitude at the eutectic composition indicating the most dynamic character of the eutectic mixture.more » MS diffusivity hence diffusion for all ion pairs increases in the system with increasing temperature. Smooth variation of the diffusivity values denies any network formation in the mixture. Also, the striking feature is the noticeable concentration dependence of MS diffusivity between cation-cation pair, Đ{sub Li-K} which remains negative for most of the concentration range but changes sign to become positive for higher LiF concentration. The negative MS diffusivity is acceptable as it satisfies the non-negative entropy constraint governed by 2{sup nd} law of thermodynamics. This high diffusivity also vouches the candidature of molten salt as a coolant.« less

Synthesis of Cation and Water Free Cryptomelane Type OMS-2 Cathode Materials: The Impact of Tunnel Water on Electrochemistry

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

Poyraz, Altug S.; Huang, Jianping; Zhang, Bingjie

Cryptomelane type manganese dioxides (α-MnO 2, OMS-2) are interesting potential cathode materials due to the ability of their one dimensional (1D) tunnels to reversibly host various cations including Li +and an accessible stable 3+/4+ redox couple. Here, we synthesized metal cation free OMS-2 materials where the tunnels were occupied by only water and hydronium ions. Water was subsequently removed from the tunnels. Cation free OMS-2 and Dry-OMS-2 were used as cathodes in Li based batteries to investigate the role of tunnel water on their electrochemistry. The initial discharge capacity was higher for Dry-OMS-2 (252 mAh/g) compared to OMS-2 (194 mAh/g),more » however, after 100 cycles Dry-OMS-2 and OMS-2 delivered 137 mAh/g and 134 mAh/g, respectively. Li +ion diffusion was more facile for Dry-OMS as evidenced by rate capability, at 400 mA/g. Dry-OMS-2 delivered 135mAh/g whereas OMS-2 delivered ~115 mAh/g. This first report of the impact of tunnel water on the electrochemistry of OMS-2 type materials demonstrates that the presence of tunnel water in OMS-2 type materials negatively impacts the electrochemistry.« less

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

PubMed

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

2018-03-21

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

Kinetics of dissolution of sapphire in melts in the CaO-Al2O3-SiO2 system

NASA Astrophysics Data System (ADS)

Shaw, Cliff S. J.; Klausen, Kim B.; Mao, Huahai

2018-05-01

The dissolution rate of sapphire in melts in the CAS system of varying silica activity, viscosity and degree of alumina saturation has been determined at 1600 °C and 1.5 GPa. After an initiation period of up to 1800 s, dissolution is controlled by diffusion of cations through the boundary layer adjacent to the dissolving sapphire. The dissolution rate decreases with increasing silica activity, viscosity and molar Al2O3/CaO. The calculated diffusion matrix for each solvent melt shows that CAS 1 and 9 which have molar Al2O3/CaO of 0.33 and 0.6 and dissolution rate constants of 0.65 × 10-6 and 0.59 × 10-6 m/s0.5 have similar directions and magnitudes of diffusive coupling: DCaO-Al2O3 and DAl2O3-CaO are both negative are approximately equal. The solvent with the fastest dissolution rate: CAS 4, which has a rate constant of 1.5 × 10-6 m/s0.5 and Al2O3/CaO of 0.31 has positive DCaO-Al2O3 and negative DAl2O3-CaO and the absolute values vary by a factor of 4. Although many studies show that aluminium is added to the melts via the reaction: Si4+ =Al3+ + 0.5Ca2+ the compositional profiles show that this reaction is not the only one involved in accommodating the aluminium added during sapphire dissolution. Rather, aluminium is incorporated as both tetrahedrally coordinated Al charge balanced by Ca and as aluminium not charge balanced by Ca (termed Alxs). This reaction: AlIV -Ca =Alxs +CaNBO where CaNBO is a non-bridging oxygen associated with calcium, may involve the formation of aluminium triclusters. The shape of the compositional profiles and oxide-oxide composition paths is controlled by the aluminium addition reaction. When Alxs exceeds 2%, CaO diffusion becomes increasingly anomalous and since the bond strength of Alxs correlates with CaO/CaO + Al2O3, the presence of more than 2% Alxs leads to significantly slower dissolution than when Alxs is absent or at low concentration. Thus, dissolution is controlled by diffusion of cations through the boundary layer, but this diffusion is itself controlled by the structural modifications required by the addition of new components to the melt. Comparison of quartz dissolution rates in similar melts shows that dissolution is much faster for quartz than for sapphire and that dissolution rates show the same correlation with silica activity and viscosity. We suggest that diffusive fluxes are related to changes in melt structure and the nature of the reaction that incorporates the added component. For the slow eigendirection, SiO2 addition occurs by a single reaction whereas Al2O3 addition requires a more complex two part reaction in which Al is accommodated by charge balance with Ca until Al is in excess of that which can be charge balanced. The Alxs incorporation reaction, is slower than the Si incorporation reaction which inhibits sapphire dissolution relative to quartz in melts of the same composition.

Maxwell-Stefan diffusion and dynamical correlation in molten LiF-KF: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Jain, Richa Naja; Chakraborty, Brahmananda; Ramaniah, Lavanya M.

2016-05-01

In this work our main objective is to compute Dynamical correlations, Onsager coefficients and Maxwell-Stefan (MS) diffusivities for molten salt LiF-KF mixture at various thermodynamic states through Green-Kubo formalism for the first time. The equilibrium molecular dynamics (MD) simulations were performed using BHM potential for LiF-KF mixture. The velocity autocorrelations functions involving Li ions reflect the endurance of cage dynamics or backscattering with temperature. The magnitude of Onsager coefficients for all pairs increases with increase in temperature. Interestingly most of the Onsager coefficients has almost maximum magnitude at the eutectic composition indicating the most dynamic character of the eutectic mixture. MS diffusivity hence diffusion for all ion pairs increases in the system with increasing temperature. Smooth variation of the diffusivity values denies any network formation in the mixture. Also, the striking feature is the noticeable concentration dependence of MS diffusivity between cation-cation pair, ĐLi-K which remains negative for most of the concentration range but changes sign to become positive for higher LiF concentration. The negative MS diffusivity is acceptable as it satisfies the non-negative entropy constraint governed by 2nd law of thermodynamics. This high diffusivity also vouches the candidature of molten salt as a coolant.

Obtaining the porewater composition of a clay rock by modeling the in- and out-diffusion of anions and cations from an in-situ experiment.

PubMed

Appelo, C A J; Vinsot, A; Mettler, S; Wechner, S

2008-10-23

A borehole in the Callovo-Oxfordian clay rock in ANDRA's underground research facility was sampled during 1 year and chemically analyzed. Diffusion between porewater and the borehole solution resulted in concentration changes which were modeled with PHREEQC's multicomponent diffusion module. In the model, the clay rock's pore space is divided in free porewater (electrically neutral) and diffuse double layer water (devoid of anions). Diffusion is calculated separately for the two domains, and individually for all the solute species while a zero-charge flux is maintained. We explain how the finite difference formulas for radial diffusion can be translated into mixing factors for solutions. Operator splitting is used to calculate advective flow and chemical reactions such as ion exchange and calcite dissolution and precipitation. The ion exchange reaction is formulated in the form of surface complexation, which allows distributing charge over the fixed sites and the diffuse double layer. The charge distribution affects pH when calcite dissolves, and modeling of the experimental data shows that about 7% of the cation exchange capacity resides in the diffuse double layer. The model calculates the observed concentration changes very well and provides an estimate of the pristine porewater composition in the clay rock.

Enhanced energy harvesting by concentration gradient-driven ion transport in SBA-15 mesoporous silica thin films.

PubMed

Hwang, Junho; Kataoka, Sho; Endo, Akira; Daiguji, Hirofumi

2016-09-21

Nanofluidic energy harvesting systems have attracted interest in the field of battery application, particularly for miniaturized electrical devices, because they possess excellent energy conversion capability for their size. In this study, a mesoporous silica (MPS)-based nanofluidic energy harvesting system was fabricated and selective ion transport in mesopores as a function of the salt gradient was investigated. Aqueous solutions with three different kinds of monovalent electrolytes-KCl, NaCl, and LiCl-with different diffusion coefficients (D + ) were considered. The highest power density was 3.90 W m -2 for KCl, followed by 2.39 W m -2 for NaCl and 1.29 W m -2 for LiCl. Furthermore, the dependency of power density on the type of cation employed indicates that the harvested energy increases as the cation mobility increases, particularly at high concentrations. This cation-specific dependency suggests that the maximum power density increases by increasing the diffusion coefficient ratio of cations to anions, making this ratio a critical parameter in enhancing the performance of nanofluidic energy harvesting systems with extremely small pores ranging from 2 to 3 nm.

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

PubMed

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

2017-01-15

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

First-Principles Analysis of Defect Thermodynamics and Ion Transport in Inorganic SEI Compounds: LiF and NaF

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

Yildirim, Handan; Kinaci, Alper; Chan, Maria K. Y.

The formation mechanism and composition of the solid electrolyte interphase (SEI) in lithium ion batteries has been widely explored. However, relatively little is known about the function of the SEI as a transport medium. Such critical information is directly relevant to battery rate performance, power loss, and capacity fading. To partially bridge this gap in the case of inorganic SEI compounds, we report herein the results of first-principles calculations on the defect thermodynamics, the dominant diffusion carriers, and the diffusion pathways associated with crystalline LiF and NaF, which are stable components of the SEI in Li-ion and Na-ion batteries, respectively.more » The thermodynamics of common point defects are computed, and the dominant diffusion carriers are determined over a voltage range of 0-4 V, corresponding to conditions relevant to both anode and cathode SEI's. Our analyses reveal that for both compounds, vacancy defects are energetically more favorable, therefore form more readily than interstitials, due to the close-packed nature of the crystal structures. However, the vacancy concentrations are very small for the diffusion processes facilitated by defects. Ionic conductivities are calculated as a function of voltage, considering the diffusion carrier concentration and the diffusion barriers as determined by nudged elastic band calculations. These conductivities are more than ten orders of magnitude smaller in NaF than in LiF. As compared to the diffusivity of Li in other common inorganic SEI compounds, such as Li2CO3 and Li2O,the cation diffusivity in LiF and NaF is quite low, with at least three orders of magnitude lower ionic conductivities. The results quantify the extent to which fluorides pose rate limitations in Li and Na batteries.« less

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

NASA Technical Reports Server (NTRS)

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

1972-01-01

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

A simulation study of CS2 solutions in two related ionic liquids with dications and monocations

NASA Astrophysics Data System (ADS)

Lynden-Bell, R. M.; Quitevis, E. L.

2018-05-01

Atomistic simulations of solutions of CS2 in an ionic liquid, [C8(C1im)2 ] [NTf2]2, with a divalent cation and in the corresponding ionic liquid with a monovalent cation, [C4C1im][NTf2], were carried out. The low-frequency librational density of states of the CS2 was of particular interest in view of recent optical heterodyne-detected Raman-induced Kerr effect spectroscopy (OHD-RIKES). Compared to the monocation ionic liquid, the maximum shifts to higher frequencies in the dication ionic liquid under ambient conditions, but was found to be significantly pressure-dependent. CS2 molecules lie above and below the plane of the imidazolium rings and found to be close to the butyl tails of the monocation. The diffusion rates and embedding energies of solvent ions and CS2 in the two ionic liquids were measured.

Role of Electrostatic Interactions on the Transport of Druglike Molecules in Hydrogel-Based Articular Cartilage Mimics: Implications for Drug Delivery.

PubMed

Ye, Fengbin; Baldursdottir, Stefania; Hvidt, Søren; Jensen, Henrik; Larsen, Susan W; Yaghmur, Anan; Larsen, Claus; Østergaard, Jesper

2016-03-07

In the field of drug delivery to the articular cartilage, it is advantageous to apply artificial tissue models as surrogates of cartilage for investigating drug transport and release properties. In this study, artificial cartilage models consisting of 0.5% (w/v) agarose gel containing 0.5% (w/v) chondroitin sulfate or 0.5% (w/v) hyaluronic acid were developed, and their rheological and morphological properties were characterized. UV imaging was utilized to quantify the transport properties of the following four model compounds in the agarose gel and in the developed artificial cartilage models: H-Ala-β-naphthylamide, H-Lys-Lys-β-naphthylamide, lysozyme, and α-lactalbumin. The obtained results showed that the incorporation of the polyelectrolytes chondroitin sulfate or hyaluronic acid into agarose gel induced a significant reduction in the apparent diffusivities of the cationic model compounds as compared to the pure agarose gel. The decrease in apparent diffusivity of the cationic compounds was not caused by a change in the gel structure since a similar reduction in apparent diffusivity was not observed for the net negatively charged protein α-lactalbumin. The apparent diffusivity of the cationic compounds in the negatively charged hydrogels was highly dependent on the ionic strength, pointing out the importance of electrostatic interactions between the diffusant and the polyelectrolytes. Solution based affinity studies between the model compounds and the two investigated polyelectrolytes further confirmed the electrostatic nature of their interactions. The results obtained from the UV imaging diffusion studies are important for understanding the effect of drug physicochemical properties on the transport in articular cartilage. The extracted information may be useful in the development of hydrogels for in vitro release testing having features resembling the articular cartilage.

Protic ammonium carboxylate ionic liquids: insight into structure, dynamics and thermophysical properties by alkyl group functionalization.

PubMed

Reddy, Th Dhileep N; Mallik, Bhabani S

2017-04-19

This study is aimed at characterising the structure, dynamics and thermophysical properties of five alkylammonium carboxylate ionic liquids (ILs) from classical molecular dynamics simulations. The structural features of these ILs were characterised by calculating the site-site radial distribution functions, g(r), spatial distribution functions and structure factors. The structural properties demonstrate that ILs show greater interaction between cations and anions when alkyl chain length increases on the cation or anion. In all ILs, spatial distribution functions show that the anion is close to the acidic hydrogen atoms of the ammonium cation. We determined the role of alkyl group functionalization of the charged entities, cations and anions, in the dynamical behavior and the transport coefficients of this family of ionic liquids. The dynamics of ILs are described by studying the mean square displacement (MSD) of the centres of mass of the ions, diffusion coefficients, ionic conductivities and hydrogen bonds as well as residence dynamics. The diffusion coefficients and ionic conductivity decrease with an increase in the size of the cation or anion. The effect of alkyl chain length on ionic conductivity calculated in this article is consistent with the findings of other experimental studies. Hydrogen bond lifetimes and residence times along with structure factors were also calculated, and are related to alkyl chain length.

Origins and implications of the ordering of oxygen vacancies and localized electrons on partially reduced CeO 2(111)

DOE PAGES

Sutton, Jonathan E.; Beste, Ariana; Steven H. Overbury

2015-10-12

In this study, we use density functional theory to explain the preferred structure of partially reduced CeO 2(111). Low-energy ordered structures are formed when the vacancies are isolated (maximized intervacancy separation) and the size of the Ce 3+ ions is minimized. Both conditions help minimize disruptions to the lattice around the vacancy. The stability of the ordered structures suggests that isolated vacancies are adequate for modeling more complex (e.g., catalytic) systems. Oxygen diffusion barriers are predicted to be low enough that O diffusion between vacancies is thermodynamically controlled at room temperature. The O-diffusion-reaction energies and barriers are decreased when onemore » Ce f electron hops from a nearest-neighbor Ce cation to a next-nearest-neighbor Ce cation, with a barrier that has been estimated to be slightly less than the barrier to O diffusion in the absence of polaron hopping. In conculsion, this indicates that polaron hopping plays a key role in facilitating the overall O diffusion process, and depending on the relative magnitudes of the polaron hopping and O diffusion barriers, polaron hopping may be the kinetically limiting process.« less

Enhanced drug transport through alginate biofilms using magnetic nanoparticles

NASA Astrophysics Data System (ADS)

McGill, Shayna L.; Cuylear, Carla; Adolphi, Natalie L.; Osinski, Marek; Smyth, Hugh

2009-02-01

The development of microbiological biofilms greatly reduces the efficacy of antibiotic therapies and is a serious problem in chronic infection and for implantable medical devices. We investigated the potential of superparamagnetic nanoparticles to increase transport through in vitro models of alginate biofilms. An in vitro alginate biofilm model was developed to mimic the composition of in vivo samples of P. aeruginosa infections. Transport through this model biofilm was performed using both bulk diffusion methods and single particle tracking techniques in the presence and absence of an external magnetic field. Bulk diffusion of nanoparticles through the biofilm was significantly enhanced in the presence of a magnetic field, both visually and quantitatively. Nanoparticle trajectories also showed transport increases were significantly higher when magnetic fields were applied. We also showed that surface chemistry (cationic, anioni, or neutral) of the nanoparticles significantly influenced transport rates. Finally, nanoparticle size also influenced the transport rates and variability of transport rates through the biofilm. In these first studies using magnetic nanoparticles in bacterial biofilms, we demonstrate that transport enhancement can be achieved and further studies are warranted.

Structural changes of polyacids initiated by their neutralization with various alkali metal hydroxides. Diffusion studies in poly(acrylic acid)s.

PubMed

Masiak, Michal; Hyk, Wojciech; Stojek, Zbigniew; Ciszkowska, Malgorzata

2007-09-27

The changes in the three-dimensional structure of the poly(acrylic acid), PAA, induced by incorporation of various alkali-metal counterions have been evaluated by studying diffusion of an uncharged probe (1,1'-ferrocenedimethanol) in the polymeric media. The studies are supported by the measurements of conductivity and viscosity of the polymeric media. Solutions of linear PAA of four different sizes (molecular weights: 450,000, 750,000, 1,250,000, 4,000,000) were neutralized with hydroxides of alkali metals of group 1 of the periodic table (Li, Na, K, Rb, Cs) to the desired neutralization degree. The transport properties of the obtained polyacrylates were monitored by measuring the changes in the probe diffusion coefficient during the titration of the polyacids. The probe diffusivity was determined from the steady-state current of the probe voltammetric oxidation at disk microelectrodes. Diffusivity of the probe increases with the increase in the degree of neutralization and with the increase in viscosity. It reaches the maximum value at about 60-80% of the polyacid neutralization. The way the probe diffusion coefficients change is similar in all polyacid solutions and gels. The increase in the size of a metal cation causes, in general, an enhancement in the transport of probe molecules. The biggest differences in the probe diffusivities are between lithium and cesium polyacrylates. The differences between the results obtained for cesium and rubidium are not statistically significant due to lack of good precision of the voltammetric measurements. The measurements of the electric conductivity of polyacrylates and the theoretical predictions supplemented the picture of electrostatic interactions between the polyanionic chains and the metal cations of increasing size. In all instances of the PAAs, the viscosity of the solutions rapidly increases in the 0-60% range of neutralization and then becomes constant in the 60-100% region. With the exception of the shortest chain polyacid, the formation of a rigid medium (gel) has been observed in the experiments with all cations. After the end point of the titration was passed, a sudden drop in the viscosity and the disappearance of the gelatinous structure were seen. The largest value of viscosity has been recorded for the longest chain polyacid. The change in the cation of the strong base used did not affect the viscosity of the polymeric system.

Investigation of local environments in Nafion-SiO(2) composite membranes used in vanadium redox flow batteries.

PubMed

Vijayakumar, M; Schwenzer, Birgit; Kim, Soowhan; Yang, Zhenguo; Thevuthasan, S; Liu, Jun; Graff, Gordon L; Hu, Jianzhi

2012-04-01

Proton conducting polymer composite membranes are of technological interest in many energy devices such as fuel cells and redox flow batteries. In particular, polymer composite membranes, such as SiO(2) incorporated Nafion membranes, are recently reported as highly promising for the use in redox flow batteries. However, there is conflicting reports regarding the performance of this type of Nafion-SiO(2) composite membrane in the redox flow cell. This paper presents results of the analysis of the Nafion-SiO(2) composite membrane used in a vanadium redox flow battery by nuclear magnetic resonance (NMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), Fourier Transform Infra Red (FTIR) spectroscopy, and ultraviolet-visible spectroscopy. The XPS study reveals the chemical identity and environment of vanadium cations accumulated at the surface. On the other hand, the (19)F and (29)Si NMR measurement explores the nature of the interaction between the silica particles, Nafion side chains and diffused vanadium cations. The (29)Si NMR shows that the silica particles interact via hydrogen bonds with the sulfonic groups of Nafion and the diffused vanadium cations. Based on these spectroscopic studies, the chemical environment of the silica particles inside the Nafion membrane and their interaction with diffusing vanadium cations during flow cell operations are discussed. This study discusses the origin of performance degradation of the Nafion-SiO(2) composite membrane materials in vanadium redox flow batteries. Copyright © 2011 Elsevier Inc. All rights reserved.

MD simulations of the formation of stable clusters in mixtures of alkaline salts and imidazolium-based ionic liquids.

PubMed

Méndez-Morales, Trinidad; Carrete, Jesús; Bouzón-Capelo, Silvia; Pérez-Rodríguez, Martín; Cabeza, Óscar; Gallego, Luis J; Varela, Luis M

2013-03-21

Structural and dynamical properties of room-temperature ionic liquids containing the cation 1-butyl-3-methylimidazolium ([BMIM](+)) and three different anions (hexafluorophosphate, [PF6](-), tetrafluoroborate, [BF4](-), and bis(trifluoromethylsulfonyl)imide, [NTf2](-)) doped with several molar fractions of lithium salts with a common anion at 298.15 K and 1 atm were investigated by means of molecular dynamics simulations. The effect of the size of the salt cation was also analyzed by comparing these results with those for mixtures of [BMIM][PF6] with NaPF6. Lithium/sodium solvation and ionic mobilities were analyzed via the study of radial distribution functions, coordination numbers, cage autocorrelation functions, mean-square displacements (including the analysis of both ballistic and diffusive regimes), self-diffusion coefficients of all the ionic species, velocity and current autocorrelation functions, and ionic conductivity in all the ionic liquid/salt systems. We found that lithium and sodium cations are strongly coordinated in two different positions with the anion present in the mixture. Moreover, [Li](+) and [Na](+) cations were found to form bonded-like, long-lived aggregates with the anions in their first solvation shell, which act as very stable kinetic entities within which a marked rattling motion of salt ions takes place. With very long MD simulation runs, this phenomenon is proved to be on the basis of the decrease of self-diffusion coefficients and ionic conductivities previously reported in experimental and computational results.

Investigation of Local Environments in Nafion-SiO2 Composite Membranes used in Vanadium Redox Flow Batteries

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

Vijayakumar, M.; Schwenzer, Birgit; Kim, Soowhan

2012-04-01

The proton conducting polymer composite membranes are of technological interest in many energy devices such as fuel cells and redox flow batteries. In particular, the polymer composite membranes such as SiO2 incorporated Nafion membranes are recently reported as highly promising for the redox flow batteries. However, there is conflicting reports regarding the performance of this Nafion-SiO2 composite membrane in the redox flow cell. This paper presents results of the analysis of the Nafion-SiO2 composite membrane used in a vanadium redox flow battery by nuclear magnetic resonance (NMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), Fourier Transformed Infra Red (FTIR) spectroscopy, and ultravioletmore » visible spectroscopy. The XPS study reveals the chemical identity and environment of vanadium cations accumulated at the surface. On the other hand, the 19F and 29Si NMR measurement explores the nature of the interaction between the silica particles, Nafion side chains and diffused vanadium cations. The 29Si NMR shows that the silica particles interaction via hydrogen bonds to the sulfonic groups of Nafion and diffused vanadium cations. Based on these spectroscopic studies, the chemical environment of the silica particles inside the Nafion membrane and their interaction with diffusing vanadium cations during flow cell operations are discussed. This study discusses the origin of performance degradation of the Nafion-SiO2 composite membrane materials in vanadium redox flow batteries.« less

Water diffusion in silicate glasses: the effect of glass structure

NASA Astrophysics Data System (ADS)

Kuroda, M.; Tachibana, S.

2016-12-01

Water diffusion in silicate melts (glasses) is one of the main controlling factors of magmatism in a volcanic system. Water diffusivity in silicate glasses depends on its own concentration. However, the mechanism causing those dependences has not been fully understood yet. In order to construct a general model for water diffusion in various silicate glasses, we performed water diffusion experiments in silica glass and proposed a new water diffusion model [Kuroda et al., 2015]. In the model, water diffusivity is controlled by the concentration of both main diffusion species (i.e. molecular water) and diffusion pathways, which are determined by the concentrations of hydroxyl groups and network modifier cations. The model well explains the water diffusivity in various silicate glasses from silica glass to basalt glass. However, pre-exponential factors of water diffusivity in various glasses show five orders of magnitude variations although the pre-exponential factor should ideally represent the jump frequency and the jump distance of molecular water and show a much smaller variation. Here, we attribute the large variation of pre-exponential factors to a glass structure dependence of activation energy for molecular water diffusion. It has been known that the activation energy depends on the water concentration [Nowak and Behrens, 1997]. The concentration of hydroxyls, which cut Si-O-Si network in the glass structure, increases with water concentration, resulting in lowering the activation energy for water diffusion probably due to more fragmented structure. Network modifier cations are likely to play the same role as water. With taking the effect of glass structure into account, we found that the variation of pre-exponential factors of water diffusivity in silicate glasses can be much smaller than the five orders of magnitude, implying that the diffusion of molecular water in silicate glasses is controlled by the same atomic process.

Consequences of acid strength for isomerization and elimination catalysis on solid acids.

PubMed

Macht, Josef; Carr, Robert T; Iglesia, Enrique

2009-05-13

We address here the manner in which acid catalysis senses the strength of solid acids. Acid strengths for Keggin polyoxometalate (POM) clusters and zeolites, chosen because of their accurately known structures, are described rigorously by their deprotonation energies (DPE). Mechanistic interpretations of the measured dynamics of alkane isomerization and alkanol dehydration are used to obtain rate and equilibrium constants and energies for intermediates and transition states and to relate them to acid strength. n-Hexane isomerization rates were limited by isomerization of alkoxide intermediates on bifunctional metal-acid mixtures designed to maintain alkane-alkene equilibrium. Isomerization rate constants were normalized by the number of accessible protons, measured by titration with 2,6-di-tert-butylpyridine during catalysis. Equilibrium constants for alkoxides formed by protonation of n-hexene increased slightly with deprotonation energies (DPE), while isomerization rate constants decreased and activation barriers increased with increasing DPE, as also shown for alkanol dehydration reactions. These trends are consistent with thermochemical analyses of the transition states involved in isomerization and elimination steps. For all reactions, barriers increased by less than the concomitant increase in DPE upon changes in composition, because electrostatic stabilization of ion-pairs at the relevant transition states becomes more effective for weaker acids, as a result of their higher charge density at the anionic conjugate base. Alkoxide isomerization barriers were more sensitive to DPE than for elimination from H-bonded alkanols, the step that limits 2-butanol and 1-butanol dehydration rates; the latter two reactions showed similar DPE sensitivities, despite significant differences in their rates and activation barriers, indicating that slower reactions are not necessarily more sensitive to acid strength, but instead reflect the involvement of more unstable organic cations at their transition states. These compensating effects from electrostatic stabilization depend on how similar the charge density in these organic cations is to that in the proton removed. Cations with more localized charge favor strong electrostatic interactions with anions and form more stable ionic structures than do cations with more diffuse charges. Ion-pairs at elimination transition states contain cations with higher local charge density at the sp(2) carbon than for isomerization transition states; as a result, these ion-pairs recover a larger fraction of the deprotonation energy, and, consequently, their reactions become less sensitive to acid strength. These concepts lead us to conclude that the energetic difficulty of a catalytic reaction, imposed by gas-phase reactant proton affinities in transition state analogues, does not determine its sensitivity to the acid strength of solid catalysts.

Influence of liquid structure on diffusive isotope separation in molten silicates and aqueous solutions

NASA Astrophysics Data System (ADS)

Watkins, James M.; DePaolo, Donald J.; Ryerson, Frederick J.; Peterson, Brook T.

2011-06-01

Molecular diffusion in natural volcanic liquids discriminates between isotopes of major ions (e.g., Fe, Mg, Ca, and Li). Although isotope separation by diffusion is expected on theoretical grounds, the dependence on mass is highly variable for different elements and in different media. Silicate liquid diffusion experiments using simple liquid compositions were carried out to further probe the compositional dependence of diffusive isotopic discrimination and its relationship to liquid structure. Two diffusion couples consisting of the mineral constituents anorthite (CaAl 2Si 2O 8; denoted AN), albite (NaAlSi 3O 8; denoted AB), and diopside (CaMgSi 2O 6; denoted DI) were held at 1450 °C for 2 h and then quenched to ambient pressure and temperature. Major-element as well as Ca and Mg isotope profiles were measured on the recovered quenched glasses. In both experiments, Ca diffuses rapidly with respect to Si. In the AB-AN experiment, D Ca/ D Si ≈ 20 and the efficiency of isotope separation for Ca is much greater than in natural liquid experiments where D Ca/ D Si ≈ 1. In the AB-DI experiment, D Ca/ D Si ≈ 6 and the efficiency of isotope separation is between that of the natural liquid experiments and the AB-AN experiment. In the AB-DI experiment, D Mg/ D Si ≈ 1 and the efficiency of isotope separation for Mg is smaller than it is for Ca yet similar to that observed for Mg in natural liquids. The results from the experiments reported here, in combination with results from natural volcanic liquids, show clearly that the efficiency of diffusive separation of Ca isotopes is systematically related to the solvent-normalized diffusivity - the ratio of the diffusivity of the cation ( D Ca) to the diffusivity of silicon ( D Si). The results on Ca isotopes are consistent with available data on Fe, Li, and Mg isotopes in silicate liquids, when considered in terms of the parameter D cation/ D Si. Cations diffusing in aqueous solutions display a similar relationship between isotopic separation efficiency and Dcation/D, although the efficiencies are smaller than in silicate liquids. Our empirical relationship provides a tool for predicting the magnitude of diffusive isotopic effects in many geologic environments and a basis for a more comprehensive theory of isotope separation in liquid solutions. We present a conceptual model for the relationship between diffusivity and liquid structure that is consistent with available data.

The influence of ionic strength on DNA diffusion in gel networks

NASA Astrophysics Data System (ADS)

Fu, Yuanxi; Jee, Ah-Young; Kim, Hyeong-Ju; Granick, Steve

Cations are known to reduce the rigidity of the DNA molecules by screening the negative charge along the sugar phosphate backbone. This was established by optical tweezer pulling experiment of immobilized DNA strands. However, little is known regarding the influence of ions on the motion of DNA molecules as they thread through network meshes. We imaged in real time the Brownian diffusion of fluorescent labeled lambda-DNA in an agarose gel network in the presence of salt with monovalent or multivalent cations. Each movie was analyzed using home-written program to yield a trajectory of center of the mass and the accompanying history of the shape fluctuations. One preliminary finding is that ionic strength has a profound influence on the slope of the trace of mean square displacement (MSD) versus time. The influence of ionic strength on DNA diffusion in gel networks.

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

PubMed Central

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

2016-01-01

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

The role of external and internal mass transfer in the process of Cu2+ removal by natural mineral sorbents.

PubMed

Sljivić, M; Smiciklas, I; Plećas, I; Pejanović, S

2011-07-01

The kinetics of Cu2+ sorption on to zeolite, clay and diatomite was investigated as a function of initial metal concentrations. For consideration of the mass transfer phenomena, single resistance models based on both film and intraparticle diffusion were tested and compared. The obtained results suggested that the rate-limiting step in Cu2+ sorption strongly depended on the sorbent type, as well as on initial cation concentration. The decrease in external mass transfer coefficients with the increase in initial metal concentrations was in excellent agreement with expressions based on Sherwood and Schmidt dimensionless numbers. The internal diffusivities through zeolite particles were in the range 1.0 x 10(-11) to 1.0 x 10(-13) m2/min, depending on the Cu2+ concentration and the applied theoretical model.

Studies on the electrodeposition of tin from acidic chloride-gluconate solutions

NASA Astrophysics Data System (ADS)

Rudnik, Ewa; Włoch, Grzegorz

2013-01-01

Electrodeposition of tin from acidic chloride-gluconate baths was investigated. Equilibrium distribution of tin(II) species showed domination of Sn(II)-gluconate complexes, but for Sn2+ concentrations 50 mM or higher increased percentage of Sn(II)-chloride complexes was found. Cyclic voltammetry, anodic stripping analysis and potentiostatic measurements indicated that rate of the cathodic process is determined by the release of metal cations from gluconate complexes in diluted bath (5 mM), but for more concentrated solutions reduction of Sn(II) ions run under diffusion control. Studies of anodic response showed that it depends on the Sn(II)/Glu ratio in the bath and deposition potential due to development of different planes of metal crystal. Average effective diffusion coefficients of metal species were determined. Morphology and structure tin deposits were also presented.

Probing dynamics and mechanism of exchange process of quaternary ammonium dimeric surfactants, 14-s-14, in the presence of conventional surfactants.

PubMed

Liu, Jun; Jiang, Yan; Chen, Hong; Mao, Shi Zhen; Du, You Ru; Liu, Mai Li

2012-12-27

In this Article, we investigated effects of different types of conventional surfactants on exchange dynamics of quaternary ammonium dimeric surfactants, with chemical formula C(14)H(29)N(+)(CH(3))(2)- (CH(2))(s)-N(+)(CH(3))(2)C(14)H(29)·2Br(-), or 14-s-14 for short. Two nonionic surfactants, TritonX-100 (TX-100) and polyethylene glycol (23) laurylether (Brij-35), and one cationic surfactant, n-tetradecyltrimethyl ammonium bromide (TTAB), and one ionic surfactant, sodium dodecyl sulfate (SDS) were chosen as typical conventional surfactants. Exchange rates of 14-s-14 (s = 2, 3, and 4) between the micelle form and monomer in solution were detected by two NMR methods: one-dimensional (1D) line shape analysis and two-dimensional (2D) exchange spectroscopy (EXSY). Results show that the nonionic surfactants (TX-100 and Brij-35), the cationic surfactant (TTAB), and the ionic surfactant (SDS) respectively accelerated, barely influenced, and slowed the exchange rate of 14-s-14. The effect mechanism was investigated by the self-diffusion experiment, relaxation time measurements (T(2)/T(1)), the fluorescence experiment (I(1)/I(3)) and observed chemical shift variations. Results reveal that, nonionic conventional surfactants (TX-100 and Brij-35) loosened the molecule arrangement and decreased hydrophobic interactions in the micelle, and thus accelerated the exchange rate of 14-s-14. The cationic conventional surfactant (TTAB) barely changed the molecule arrangement and thus barely influenced the exchange rate of 14-s-14. The ionic conventional surfactant (SDS) introduced the electrostatic attraction effect, tightened the molecule arrangement, and increased hydrophobic interactions in the micelle, and thus slowed down the exchange rate of 14-s-14. Additionally, the two-step exchange mechanism of 14-s-14 in the mixed solution was revealed through interesting variation tendencies of exchange rates of 14-s-14.

Effects of spin transition on diffusion of Fe2+ in ferropericlase in Earth's lower mantle

NASA Astrophysics Data System (ADS)

Saha, Saumitra; Bengtson, Amelia; Crispin, Katherine L.; van Orman, James A.; Morgan, Dane

2011-11-01

Knowledge of Fe composition in lower-mantle minerals (primarily perovskite and ferropericlase) is essential to a complete understanding of the Earth's interior. Fe cation diffusion potentially controls many aspects of the distribution of Fe in the Earth's lower mantle, including mixing of chemical heterogeneities, element partitioning, and the extent of core-mantle communications. Fe in ferropericlase has been shown to undergo a spin transition starting at about 40 GPa and exists in a mixture of high-spin and low-spin states over a wide range of pressures. Present experimental data on Fe transport in ferropericlase is limited to pressures below 35 GPa and provides little information on the pressure dependence of the activation volume and none on the impact of the spin transition on diffusion. Therefore, known experimental data on Fe diffusion cannot be reliably extrapolated to predict diffusion throughout the lower mantle. Here, first-principles and statistical modeling are combined to predict diffusion of Fe in ferropericlase over the entire lower mantle, including the effects of the Fe spin transition. A thorough statistical thermodynamic treatment is given to fully incorporate the coexistence of high- and low-spin Fe in the model of overall Fe diffusion in the lower mantle. Pure low-spin Fe diffuses approximately 104 times slower than high-spin Fe in ferropericlase but Fe diffusion of the mixed-spin state is only about 10 times slower than that of high-spin Fe. The predicted Fe diffusivities demonstrate that ferropericlase is unlikely to be rate limiting in transporting Fe in deep earth since much slower Fe diffusion in perovskite is predicted.

Role of Reverse Divalent Cation Diffusion in Forward Osmosis Biofouling.

PubMed

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

2015-11-17

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

Do TFSA anions slither? Pressure exposes the role of TFSA conformational exchange in self-diffusion

DOE PAGES

Suarez, Sophia N.; Wishart, James F.; Rua, Armando; ...

2015-10-28

Multi-nuclear ( 1H, 2H, and 19F) magnetic resonance spectroscopy techniques as functions of temperature and pressure were applied to the study of selectively deuterated 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (EMIM TFSA) ionic liquid isotopologues and related ionic liquids. For EMIM TFSA, temperature-dependent 2H T 1 data indicate stronger electric field gradients in the alkyl chain region compared to the imidazolium ring. Most significantly, the pressure dependences of the EMIM and TFSA self-diffusion coefficients revealed that the displacements of the cations and anions are independent, with diffusion of the TFSA anions being slowed much more by increasing pressure than for the EMIM cations, asmore » shown by their respective activation volumes (28.8 ± 2.5 cm³/mol for TFSA vs. 14.6 ± 1.3 cm³/mol for EMIM). Increasing pressure may lower the mobility of the TFSA anion by hindering its interconversion between trans and cis conformers, a process that is coupled to diffusion according to published molecular dynamics simulations. Measured activation volumes (ΔV ‡) for ion self-diffusion in EMIM bis(fluoromethylsulfonyl)amide and EMIM tetrafluoroborate support this hypothesis.« less

Do TFSA anions slither? Pressure exposes the role of TFSA conformational exchange in self-diffusion

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

Suarez, Sophia N.; Wishart, James F.; Rua, Armando

Multi-nuclear ( 1H, 2H, and 19F) magnetic resonance spectroscopy techniques as functions of temperature and pressure were applied to the study of selectively deuterated 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (EMIM TFSA) ionic liquid isotopologues and related ionic liquids. For EMIM TFSA, temperature-dependent 2H T 1 data indicate stronger electric field gradients in the alkyl chain region compared to the imidazolium ring. Most significantly, the pressure dependences of the EMIM and TFSA self-diffusion coefficients revealed that the displacements of the cations and anions are independent, with diffusion of the TFSA anions being slowed much more by increasing pressure than for the EMIM cations, asmore » shown by their respective activation volumes (28.8 ± 2.5 cm³/mol for TFSA vs. 14.6 ± 1.3 cm³/mol for EMIM). Increasing pressure may lower the mobility of the TFSA anion by hindering its interconversion between trans and cis conformers, a process that is coupled to diffusion according to published molecular dynamics simulations. Measured activation volumes (ΔV ‡) for ion self-diffusion in EMIM bis(fluoromethylsulfonyl)amide and EMIM tetrafluoroborate support this hypothesis.« less

Communication: Unusual structure and transport in ionic liquid-hexane mixtures

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

Liang, Min; Khatun, Sufia; Castner, Edward W., E-mail: ecastner@rci.rutgers.edu

2015-03-28

Ionic liquids having a sufficiently amphiphilic cation can dissolve large volume fractions of alkanes, leading to mixtures with intriguing properties on molecular length scales. The trihexyl(tetradecyl)phosphonium cation paired with the bis(trifluoromethylsulfonyl)amide anion provides an ionic liquid that can dissolve large mole fractions of hexane. We present experimental results on mixtures of n-C{sub 6}D{sub 14} with this ionic liquid. High-energy X-ray scattering studies reveal a persistence of the characteristic features of ionic liquid structure even for 80% dilution with n-C{sub 6}D{sub 14}. Nuclear magnetic resonance self-diffusion results reveal decidedly non-hydrodynamic behavior where the self-diffusion of the neutral, non-polar n-C{sub 6}D{sub 14}more » is on average a factor of 21 times faster than for the cation. Exploitation of the unique structural and transport properties of these mixtures may lead to new opportunities for designer solvents for enhanced chemical reactivity and interface science.« less

Communication: Unusual structure and transport in ionic liquid-hexane mixtures

DOE PAGES

Liang, Min; Khatun, Sufia; Castner, Edward W.

2015-03-28

Ionic liquids having a sufficiently amphiphilic cation can dissolve large volume fractions of alkanes, leading to mixtures with intriguing properties on molecular length scales. The trihexyl(tetradecyl)phosphonium cation paired with the bis(trifluoromethylsulfonyl)amide anion provides an ionic liquid that can dissolve large mole fractions of hexane. We present experimental results on mixtures of n-C 6D 14 with this ionic liquid. High- energy X-ray scattering studies reveal a persistence of the characteristic features of ionic liquid structure even for 80% dilution with n-C 6D 14. NMR self-diffusion results reveal decidedly non-hydrodynamic behavior where the self-diffusion of the neutral, non-polar n-C 6D 14 ismore » on average a factor of 21 times faster than for the cation. Exploitation of the unique structural and transport properties of these mixtures may lead to new opportunities for designer solvents for enhanced chemical reactivity and interface science.« less

Enhancing the Ion Transport in LiMn1.5Ni0.5O4 by Altering the Particle Wulff Shape via Anisotropic Surface Segregation.

PubMed

Huang, Jiajia; Liu, Haodong; Zhou, Naixie; An, Ke; Meng, Ying Shirley; Luo, Jian

2017-10-25

Spontaneous and anisotropic surface segregation of W cations in LiMn 1.5 Ni 0.5 O 4 particles can alter the Wulff shape and improve surface stability, thereby significantly improving the electrochemical performance. An Auger electron nanoprobe was employed to identify the anisotropic surface segregation, whereby W cations prefer to segregate to {110} surface facets to decrease its relative surface energy according to Gibbs adsorption theory and subsequently increase its surface area according to Wulff theory. Consequently, the rate performance is improved (e.g., by ∼5-fold at a high rate of 25C) because the {110} facets have more open channels for fast lithium ion diffusion. Furthermore, X-ray photoelectron spectroscopy (XPS) depth profiling suggested that the surface segregation and partial reduction of W cation inhibit the formation of Mn 3+ on surfaces to improve cycling stability via enhancing the cathode electrolyte interphase (CEI) stability at high charging voltages. This is the first report of using anisotropic surface segregation to thermodynamically control the particle morphology as well as enhancing CEI stability as a facile, and potentially general, method to significantly improve the electrochemical performance of battery electrodes. Combining neutron diffraction, an Auger electron nanoprobe, XPS, and other characterizations, we depict the underlying mechanisms of improved ionic transport and CEI stability in high-voltage LiMn 1.5 Ni 0.5 O 4 spinel materials.

Thermodynamics and defect chemistry of substitutional and interstitial cation doping in layered α-V2O5.

PubMed

McColl, Kit; Johnson, Ian; Corà, Furio

2018-05-25

A systematic study of the location and energetics of cation dopants in α-V2O5 has been conducted using pair-potential methods, supplemented by first-principles calculations. The consequences of doping on intrinsic defect equilibria have been discussed and the effects of selected dopants on Li+ and Mg2+ diffusion energy barriers have been investigated.

Oxidation of silicon nitride sintered with rare-earth oxide additions

NASA Technical Reports Server (NTRS)

Mieskowski, D. M.; Sanders, W. A.

1985-01-01

The effects of rare-earth oxide additions on the oxidation of sintered Si3N4 were examined. Insignificant oxidation occurred at 700 and 1000 C, with no evidence of phase instability. At 1370 C, the oxidation rate was lowest for Y2O3 and increased for additions of La2O3, Sm2O3, and CeO2, in that order. Data obtained from X-ray diffraction, electron microprobe analysis, and scanning electron microscopy indicate that oxidation occurs via diffusion of cationic species from Si3N4 grain boundaries.

Physical properties of ionic liquids consisting of the 1-butyl-3-methylimidazolium cation with various anions and the bis(trifluoromethylsulfonyl)imide anion with various cations.

PubMed

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

2008-01-10

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

Structure and Dynamics of Ionic Liquid [MMIM][Br] Confined in Hydrophobic and Hydrophilic Porous Matrices: A Molecular Dynamics Simulation Study.

PubMed

Sharma, Anirban; Ghorai, Pradip Kr

2016-11-17

The effects of confinement on the structural and dynamical properties of the ionic liquid (IL) 1,3-dimethylimidazolium bromide ([MMIM][Br]) have been investigated by molecular dynamics simulations. We used zeolite faujasite (NaY) as a hydrophilic confinement and dealuminated faujasite (DAY) as a hydrophobic confinement. The presence of an extra framework cation, [Na + ], in NaY makes the host hydrophilic, whereas DAY, with no extra framework cation, is hydrophobic. Although both NaY and DAY have almost similar structures, the IL showed markedly different structural and dynamical properties in these confinements and in bulk. In the confinements, the cation-cation radial distribution function, which strongly depends on temperature, exhibits a layer-like structure, whereas in bulk, it shows a liquid-like structure that hardly depends on temperature. Although the interaction between [MMIM] + and Br - in DAY is stronger than that in both NaY and bulk, the strength of the interaction between them is almost invariant with temperature. Both [MMIM] + and Br - strongly interact with Na + of the host, and their interaction strongly depends on temperature, whereas the interaction of the IL with Si and O is very weak and invariant with temperature. In bulk, the self-diffusion coefficient, [D], of both [MMIM] + and Br - increases exponentially with temperature, and the D of the cation is slightly higher than that of the anion at all studied temperatures, whereas in the confinements, [MMIM] + moves much faster than Br - . For example, in the hydrophilic confinement, the D of the cation is 20-30 times higher than that of the anion. The D of both the ions decreases significantly in the confinements as compared to that in bulk. During diffusion, [MMIM] + diffuses closer to the inner surface in the hydrophilic confinement than that in the hydrophobic confinement. The diffusion pathway imperceptibly depends on temperature but strongly depends on the nature of the confinement. The self part of the time-dependent van Hoove correlation function of [MMIM] + in the hydrophilic confinement shows a larger deviation from its Gaussian form than that in the hydrophobic confinement at all temperatures, indicating that the long-time dynamics of [MMIM] + in NaY is more heterogeneous than that in DAY. Although the orientational relaxation time scales of [MMIM] + in the confinements significantly slowed as compared to those in bulk, confinement does not affect the librational motion of the collective hydrogen-bond network present in the IL.

The cooling rate dependence of cation distributions in CoFe2O4

NASA Technical Reports Server (NTRS)

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

1989-01-01

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

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

PubMed

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

2014-09-09

The utilization of Amberlite (IRP-69 ion-exchange resin, 100-500 wet mesh) as the binding phase in the diffusive gradients in thin films (DGT) technique has shown potential to improve the assessment of plant-available K in soils. The binding phase has recently been optimized by using a mixed Amberlite and ferrihydrite (MAF) gel which results in linear K uptake over extended deployment periods and in solutions with higher K concentrations. As restriction of K uptake by Ca on the Amberlite based resin gel has been previously proposed, potential competing effects of Ca(2+), Mg(2+) and NH(4+) on K uptake by the MAF gel were investigated. These cations had no effect on K elution efficiency which was 85%. However, K uptake by the MAF gel was restricted in the presence of competing cations in solution. Consequently, the diffusion coefficient of K decreased in the presence of cations compared to previous studies but was stable at 1.12×10(-5)cm(2)s(-1) at 25°C regardless of cation concentrations. Uptake of K by the DGT device was affected by the presence of excessive Ca in more than 30% of twenty typical Australian agricultural soils. However, this problem could be circumvented by using a shorter deployment time than the normal 24 h. Moderate correlation of concentrations of K extracted by DGT with Colwell K (extracted by NaHCO(3), R(2)=0.69) and NH4OAc K (R(2)=0.61) indicates that DGT measures a different pool of K in soils than that measured by the standard extractants used. In addition, the MAF gel has the ability to measure Ca and Mg simultaneously. Copyright © 2014 Elsevier B.V. All rights reserved.

Isotope fractionation by multicomponent diffusion (Invited)

NASA Astrophysics Data System (ADS)

Watkins, J. M.; Liang, Y.; Richter, F. M.; Ryerson, F. J.; DePaolo, D. J.

2013-12-01

Isotope fractionation by multicomponent diffusion The isotopic composition of mineral phases can be used to probe the temperatures and rates of mineral formation as well as the degree of post-mineralization alteration. The ability to interpret stable isotope variations is limited by our knowledge of three key parameters and their relative importance in determining the composition of a mineral grain and its surroundings: (1) thermodynamic (equilibrium) partitioning, (2) mass-dependent diffusivities, and (3) mass-dependent reaction rate coefficients. Understanding the mechanisms of diffusion and reaction in geological liquids, and how these mass transport processes discriminate between isotopes, represents an important problem that is receiving considerable attention in the geosciences. Our focus in this presentation will be isotope fractionation by chemical diffusion. Previous studies have documented that diffusive isotope effects vary depending on the cation as well as the liquid composition, but the ability to predict diffusive isotope effects from theory is limited; for example, it is unclear whether the magnitude of diffusive isotopic fractionations might also vary with the direction of diffusion in composition space. To test this hypothesis and to further guide the theoretical treatment of isotope diffusion, two chemical diffusion experiments and one self diffusion experiment were conducted at 1250°C and 0.7 GPa. In one experiment (A-B), CaO and Na2O counter-diffuse rapidly in the presence of a small SiO2 gradient. In the other experiment (D-E), CaO and SiO2 counter-diffuse more slowly in a small Na2O gradient. In both chemical diffusion experiments, Ca isotopes become fractionated by chemical diffusion but by different amounts, documenting for the first time that the magnitude of isotope fractionation by diffusion depends on the direction of diffusion in composition space. The magnitude of Ca isotope fractionation that develops is positively correlated with the rate of CaO diffusion; in A-B, the total variation is 2.5‰ whereas in D-E it is only 1.3‰. The diffusion of isotopes in a multicomponent system is modeled using a new expression for the isotope-specific diffusive flux that includes self diffusion terms in addition to the multicomponent chemical diffusion matrix. Kinetic theory predicts a mass dependence on isotopic mobility, i.e., self diffusivity, but it is unknown whether or how the mass dependence on self diffusivity translates into a mass dependence on chemical diffusion coefficients. The new experimental results allow us to assess several empirical expressions relating the self diffusivity and its mass dependence to the elements of the diffusion matrix and their mass dependence. Several plausible theoretical treatments can fit the data equally well. We are currently at the stage where experiments are guiding the theoretical treatment of the isotope fractionation by diffusion problem, underscoring the importance of experiments for aiding interpretations of isotopic variations in nature.

Near-Infrared-Emitting CuInS2/ZnS Dot-in-Rod Colloidal Heteronanorods by Seeded Growth

PubMed Central

2018-01-01

Synthesis protocols for anisotropic CuInX2 (X = S, Se, Te)-based heteronanocrystals (HNCs) are scarce due to the difficulty in balancing the reactivities of multiple precursors and the high solid-state diffusion rates of the cations involved in the CuInX2 lattice. In this work, we report a multistep seeded growth synthesis protocol that yields colloidal wurtzite CuInS2/ZnS dot core/rod shell HNCs with photoluminescence in the NIR (∼800 nm). The wurtzite CuInS2 NCs used as seeds are obtained by topotactic partial Cu+ for In3+ cation exchange in template Cu2–xS NCs. The seed NCs are injected in a hot solution of zinc oleate and hexadecylamine in octadecene, 20 s after the injection of sulfur in octadecene. This results in heteroepitaxial growth of wurtzite ZnS primarily on the Sulfur-terminated polar facet of the CuInS2 seed NCs, the other facets being overcoated only by a thin (∼1 monolayer) shell. The fast (∼21 nm/min) asymmetric axial growth of the nanorod proceeds by addition of [ZnS] monomer units, so that the polarity of the terminal (002) facet is preserved throughout the growth. The delayed injection of the CuInS2 seed NCs is crucial to allow the concentration of [ZnS] monomers to build up, thereby maximizing the anisotropic heteroepitaxial growth rates while minimizing the rates of competing processes (etching, cation exchange, alloying). Nevertheless, a mild etching still occurred, likely prior to the onset of heteroepitaxial overgrowth, shrinking the core size from 5.5 to ∼4 nm. The insights provided by this work open up new possibilities in designing multifunctional Cu-chalcogenide based colloidal heteronanocrystals. PMID:29569443

The role of halide ions on the electrochemical behaviour of iron in alkali solutions

NASA Astrophysics Data System (ADS)

Begum, S. Nathira; Muralidharan, V. S.; Basha, C. Ahmed

2008-02-01

Active dissolution and passivation of transition metals in alkali solutions is of technological importance in batteries. The performance of alkaline batteries is decided by the presence of halides as they influence passivation. Cyclic voltammetric studies were carried out on iron in different sodium hydroxide solutions in presence of halides. In alkali solutions iron formed hydroxo complexes and their polymers in the interfacial diffusion layer. With progress of time they formed a cation selective layer. The diffusion layer turned into bipolar ion selective layer consisted of halides, a selective inner sublayer to the metal side and cation selective outer layer to the solution side. At very high anodic potentials, dehydration and deprotonation led to the conversion of salt layer into an oxide.

Preparation and Analysis of RNA Crystals

NASA Technical Reports Server (NTRS)

Todd, Paul

2000-01-01

The crystallization of RiboNucleic Acids (RNA) was studied from the standpoint of mechanisms of crystal growth in three tasks: (1) preparation of high-quality crystals of oligonuclotides for X-ray diffraction, (2) finding pathways to the growth of high-quality crystals for X-ray diffraction and (3) investigation of mechanisms of action of inertial acceleration on crystal growth. In these tasks: (1) RNA crystals were prepared and studied by X-ray diffraction; (2) a pathway to high-quality crystals was discovered and characterized; a combination of kinetic and equilibrium factors could be optimized as described below; and (3) an interplay between purity and gravity was found in a combination of space and ground experiments with nucleic acids and proteins. Most significantly, the rate of concentration of precipitant and RNA can be controlled by membrane-based methods of water removal or by diffusion of multivalent cations across an interface stabilized by a membrane. Oligonucleotide solutions are electrokinetically stabilized colloids, and crystals can form by the controlled addition of multivalent cations.

Solution of the nonlinear Poisson-Boltzmann equation: Application to ionic diffusion in cementitious materials

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

Arnold, J.; Kosson, D.S., E-mail: david.s.kosson@vanderbilt.edu; Garrabrants, A.

2013-02-15

A robust numerical solution of the nonlinear Poisson-Boltzmann equation for asymmetric polyelectrolyte solutions in discrete pore geometries is presented. Comparisons to the linearized approximation of the Poisson-Boltzmann equation reveal that the assumptions leading to linearization may not be appropriate for the electrochemical regime in many cementitious materials. Implications of the electric double layer on both partitioning of species and on diffusive release are discussed. The influence of the electric double layer on anion diffusion relative to cation diffusion is examined.

Synthetic control of manganese birnessite: Impact of crystallite size on Li, Na, and Mg based electrochemistry

DOE PAGES

Yin, Jiefu; Takeuchi, Esther S.; Takeuchi, Kenneth J.; ...

2016-08-12

We demonstrated the synthesis and characterization of Mg-birnessite (Mg xMnO 2) with different crystallite sizes, prepared though low temperature precipitation and ion exchange. The influence of crystallite size on electrochemical performance of Mg-birnessite was studied for the first time, where material with smaller crystallite size was demonstrated to have enhanced capacity and rate capability in Li ion, Na ion, and Mg ion based electrolytes. Cation diffusion using GITT type testing demonstrated the ion diffusion coefficient of Mg 2+ was ~10× lower compared with Li + and Na +. This work illustrates that tuning of inorganic materials properties can lead tomore » significant enhancement of electrochemical performance in lithium, sodium as well as magnesium based batteries for materials such as Mg-birnessite and provides a deliberate approach to improve electrochemical performance.« less

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

PubMed

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

2012-08-15

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

Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids

DOE PAGES

Wu, Boning; Liang, Min; Maroncelli, Mark; ...

2015-10-26

Ionic liquids with electron-donating anions are used to investigate rates and mechanisms of photoinduced bimolecular electron transfer to the photoexcited acceptor 9,10-dicyanoanthracene (9,10-DCNA). The set of five cyano anion ILs studied comprises the 1-ethyl-3-methylimidazolium cation paired with each of these five anions: selenocyanate, thiocyanate, dicyanamide, tricyanomethanide, and tetracyano-borate. Measurements with these anions dilute in acetonitrile and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-amide show that the selenocyanate and tricyanomethanide anions are strong quenchers of the 9,10-DCNA fluorescence, thiocyanate is a moderately strong quencher, dicyanamide is a weak quencher, and no quenching is observed for tetracyanoborate. Quenching rates are obtained from both time-resolved fluorescence transients andmore » time-integrated spectra. Finally, application of a Smoluchowski diffusion-and-reaction model showed that the complex kinetics observed can be fit using only two adjustable parameters, D and V 0, where D is the relative diffusion coefficient between donor and acceptor and V 0 is the value of the electronic coupling at donor-acceptor contact.« less

Viscosity, conductivity, and electrochemical property of dicyanamide ionic liquids

NASA Astrophysics Data System (ADS)

Yuan, Wen-Li; Yang, Xiao; He, Ling; Xue, Ying; Qin, Song; Tao, Guo-Hong

2018-03-01

The instructive structure-property relationships of ionic liquids (ILs) can be put to task-specific design of new functionalized ILs. The dicyanamide (DCA) ILs are typical CHN type ILs which are halogen free, chemical stable, low-viscous and fuel-rich. The transport properties of DCA ionic liquids are significant for their applications as solvents, electrolytes and hypergolic propellants. This work systematically investigates several important transport properties of four DCA ILs ([C4mim][N(CN)2], [C4m2im][N(CN)2], N4442[N(CN)2], and N8444[N(CN)2]) including viscosity, conductivity, and electrochemical property at different temperatures. The melting points, temperature-dependent viscosities and conductivities reveal the structure-activity relationship of four DCA ILs. From the Walden plots, the imidazolium cations exhibit stronger cation–anion attraction than the ammonium cations. DCA ILs have relatively high values of electrochemical windows (EWs), which indicates that the DCA ILs are potential candidates for electrolytes in electrochemical applications. The cyclic voltammograms of Eu(III) in these DCA ILs at GC working electrode at various temperatures 303–333 K consists of quasi-reversible waves. The electrochemical properties of the DCA ILs are also dominated by the cationic structures. The current intensity (ip), the diffusion coefficients (Do), the charge transfer rate constants (ks) of Eu(III) in DCA ILs all increased with the molar conductivities increased. The cationic structure-transport property relationships of DCA ILs were constructed for designing novel functionalized ILs to fulfill specific demands.

Viscosity, Conductivity, and Electrochemical Property of Dicyanamide Ionic Liquids

PubMed Central

Yuan, Wen-Li; Yang, Xiao; He, Ling; Xue, Ying; Qin, Song; Tao, Guo-Hong

2018-01-01

The instructive structure-property relationships of ionic liquids (ILs) can be put to task-specific design of new functionalized ILs. The dicyanamide (DCA) ILs are typical CHN type ILs which are halogen free, chemical stable, low-viscous, and fuel-rich. The transport properties of DCA ionic liquids are significant for their applications as solvents, electrolytes, and hypergolic propellants. This work systematically investigates several important transport properties of four DCA ILs ([C4mim][N(CN)2], [C4m2im][N(CN)2], N4442[N(CN)2], and N8444[N(CN)2]) including viscosity, conductivity, and electrochemical property at different temperatures. The melting points, temperature-dependent viscosities and conductivities reveal the structure-activity relationship of four DCA ILs. From the Walden plots, the imidazolium cations exhibit stronger cation–anion attraction than the ammonium cations. DCA ILs have relatively high values of electrochemical windows (EWs), which indicates that the DCA ILs are potential candidates for electrolytes in electrochemical applications. The cyclic voltammograms of Eu(III) in these DCA ILs at GC working electrode at various temperatures 303–333 K consists of quasi-reversible waves. The electrochemical properties of the DCA ILs are also dominated by the cationic structures. The current intensity (ip), the diffusion coefficients (Do), the charge transfer rate constants (ks) of Eu(III) in DCA ILs all increased with the molar conductivities increased. The cationic structure-transport property relationships of DCA ILs were constructed for designing novel functionalized ILs to fulfill specific demands. PMID:29600245

Enhancing thermoelectrochemical properties by tethering ferrocene to the anion or cation of ionic liquids: altered thermodynamics and solubility.

PubMed

Aldous, Leigh; Black, Jeffrey J; Elias, Maximo C; Gélinas, Bruno; Rochefort, Dominic

2017-09-13

Entropic changes inherent within a redox process typically result in significant temperature sensitivity. This can be utilised positively or can be a detrimental process. This study has investigated the thermoelectrochemical properties (temperature-dependant electrochemistry) of the ferrocenium|ferrocene redox couple in an ionic liquid, and in particular the effect of covalently tethering this redox couple to fixed positive or negative charges. As such, the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide was employed to dissolve ferrocene, as well as cationic-tethered ferrocene (the 1-ethyl-3-(methylferrocenyl)imidazolium cation) and anionic-tethered ferrocene (the ferrocenylsulfonyl(trifluoromethylsulfonyl)imide anion). These systems were characterised in terms of their voltammetry (apparent formal potentials, diffusion coefficients and electron transfer rate constants) and thermoelectrochemistry (temperature coefficients of the cell potential or 'Seebeck coefficients', short circuit current densities and power density outputs). The oxidised cationic species behaved like a dicationic species and was thus 6-fold more effective at converting waste thermal energy to electrical power within a thermoelectrochemical cell than unmodified ferrocene. This was almost exclusively due to a significant boost in the Seebeck coefficient of this redox couple. Conversely, the oxidised anionic species was formally a zwitterion, but this zwitterionic species behaved thermodynamically like a neutral species. The inverted entropic change upon going from ferrocene to anion-tethered ferrocene allowed development of a largely temperature-insensitive reference potential based upon a mixture of acetylferrocene and ferricenyl(iii)sulfonyl(trifluoromethylsulfonyl)imide.

Nucleation and growth kinetics of electrodeposited sulfate-doped polypyrrole: determination of the diffusion coefficient of SO(4)(2-) in the polymeric membrane.

PubMed

Licona-Sánchez, T de J; Alvarez-Romero, G A; Mendoza-Huizar, L H; Galán-Vidal, C A; Palomar-Pardavé, M; Romero-Romo, M; Herrera-Hernández, H; Uruchurtu, J; Juárez-García, J M

2010-08-05

A kinetic study for the electrosynthesis of polypyrrole (Ppy) doped with SO(4)(2-) ions is presented. Ppy films were electrochemically polymerized onto a graphite-epoxy resin electrode. Experimental current density transients (j-t) were obtained for three different potentiometric behaviors: anionic, cationic, and a combination. Theoretical models were used to fit the experimental j-t data to determine the nucleation and growth processes controlling the polymer synthesis. It was encountered that, in all cases, pyrrole electropolimerization involves two concomitant processes, namely, a Ppy diffusion limited multiple 3D nucleation and growth and pyrrole electro-oxidation on the growing surface of the Ppy nuclei. SEM analysis of the electrodes surfaces reveals that Ppy deposition occurred over most of the electrode surface by multiple nucleation of hemispheres, as the theoretical model used for the analysis of the current transients required. Hemispherical particles formed the polymeric film displaying different sizes. The order for the particle size was as follows: anionic > anionic-cationic > cationic. These results are congruent with those obtained by theoretical analysis of the corresponding current transients. Analysis of the impedance measurements recorded on the anionic Ppy film, immersed in an aqueous solution with different sulfate ion concentrations evidenced that SO(4)(2-) ions diffuse through the Ppy film provoking a decrease of its electrical resistance and an increase of its dielectric constant. From the Warburg impedance coefficient, the sulfate coefficient of diffusion in the Ppy film was 1.38 x 10(-9) cm(2) s(-1).

Effect of low frequency, low amplitude magnetic fields on the permeability of cationic liposomes entrapping carbonic anhydrase: II. No evidence for surface enzyme involvement.

PubMed

Ramundo-Orlando, A; Mattia, F; Palombo, A; D'Inzeo, G

2000-10-01

Observations recently reported by our group indicate that combined 7 Hz sinusoidal (B(acpeak) = 50 mu T) and parallel static (B(dc) = 50 mu T) magnetic fields can induce a significant increase in diffusion rate of substrate across carbonic anhydrase (CA)-loaded liposomes (DPPC:Chol:SA). A direct involvement of charges of stearylamine (SA) on the lipid membrane surface was also demonstrated. Kinetic studies showed that CA was mainly entrapped in liposomes at 5:3:2 molar ratio, although a small amount (17%) of enzyme was also located on the external surface of these cationic liposomes. In this paper we report steady state kinetic studies on this latter CA after ELF-EMFs exposure. No difference in the apparent K(m) between exposed and sham samples was observed. On the contrary the apparent V(max) was increased by approximately a factor of 2 after field exposure. In spite of the proteolytic digestion of this external CA, a significant increase of enzymatic activity, as a function of increase in the diffusion rate of substrate across the lipid bilayer, was observed in the exposed samples. Based on these results, a conformational change induced by the field on the CA located on the external surface of 5:3:2 liposomes is excluded as an explanation for our previous observations, supporting the primary role of bilayer SA in the interaction with ELF. A model of ELF interaction, based on the Larmor precession theory, explaining the physical phenomenon induced on the dipole of SA has been developed. Copyright 2000 Wiley-Liss, Inc.

Structural and photodynamic properties of the anti-cancer drug irinotecan in aqueous solutions of different pHs.

PubMed

di Nunzio, Maria Rosaria; Douhal, Yasmin; Organero, Juan Angel; Douhal, Abderrazzak

2018-05-23

This work reports on photophysical studies of the irinotecan (IRT) anti-cancer drug in water solutions of different acidities (pH = 1.11-9.46). We found that IRT co-exists as mono-cationic (C1), di-cationic (C2), or neutral (N) forms. The population of each prototropic species depends on the pH of the solution. At pH = 1.11-3.01, the C1 and C2 structures are stabilized. At pH = 7.00, the most populated species is C1, while at pH values larger than 9.46 the N form is the most stable species. In the 1.11-2.61 pH range, the C1* emission is efficiently quenched by protons to give rise to the emission from C2*. The dynamic quenching constant, KD, is ∼32 M-1. While the diffusion governs the rate of excited-state proton-transfer (ESPT) under these conditions, the reaction rate increases with the proton concentration. A two-step diffusive Debye-Smoluchowski model was applied at pH = 1.11-2.61 to describe the protonation of C1*. The ESPT time constants derived for C1* are 382 and 1720 ps at pH = 1.11 and 1.95, respectively. We found that one proton species is involved in the protonation of C1* to give C2*, in the analyzed acidic pH range. Under alkaline conditions (pH = 9.46), the N form is the most stable structure of IRT. These results indicate the influence of the pH of the medium on the structural and dynamical properties of IRT in water solution. They may help to provide a better understanding on the relationship between the structure and biological activity of IRT.

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

PubMed

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

2016-06-30

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

Ion Transport and Structural Properties of Polymeric Electrolytes and Ionic Liquids from Molecular Dynamics Simulations

NASA Astrophysics Data System (ADS)

Borodin, Oleg

2010-03-01

Molecular dynamics simulations are well suited for exploring electrolyte structure and ion transport mechanisms on the nanometer length scale and the nanosecond time scales. In this presentation we will describe how MD simulations assist in answering fundamental questions about the lithium transport mechanisms in polymeric electrolytes and ionic liquids. In particular, in the first part of the presentation the extent of ion aggregation, the structure of ion aggregates and the lithium cation diffusion in binary polymeric electrolytes will be compared with that of single-ion conducting polymers. In the second part of the talk, the lithium transport in polymeric electrolytes will be compared with that of three ionic liquids ( [emim][FSI] doped with LiFSI , [pyr13][FSI] doped with LiFSI, [emim][BF4] doped with LiBF4). The relation between ionic liquid self-diffusion, conductivity and thermodynamic properties will be discussed in details. A number of correlations between heat of vaporization Hvap, cation-anion binding energy (E+/-), molar volume (Vm), self-diffusion coefficient (D) and ionic conductivity for 29 ionic liquids have been investigated using MD simulations. A significant correlation between D and Hvap has been found, while best correlation was found for -log((D Vm)) vs. Hvap+0.28E+/-. A combination of enthalpy of vaporization and a fraction of the cation-anion binding energy was suggested as a measure of the effective cohesive energy for ionic liquids.

An experimental and modeling study of grain-scale uranium desorption from field-contaminated sediments and the potential influence of microporosity on mass-transfer

NASA Astrophysics Data System (ADS)

Stoliker, D.; Liu, C.; Kent, D. B.; Zachara, J. M.

2012-12-01

The aquifer below the 300-Area of the Hanford site (Richland, WA, USA) is plagued by a persistent plume of dissolved uranium (U(VI)) in excess of the Environmental Protection Agency drinking water maximum contamination level even after the removal of highly contaminated sediments. The aquifer sediments in the seasonally saturated lower vadose zone act as both a source and sink for uranium during stage changes in the nearby Columbia River. Diffusion limitation of uranium mass-transfer within these sediments has been cited as a potential cause of the plume's persistence. Equilibrium U(VI) sorption is a strong function of variable chemical conditions, especially carbonate, hydrogen, and uranyl ion activities. Field-contaminated sediments from the site require up to 1,000 hours to reach equilibrium in static batch reactors. Increases in U(VI) concentrations over longer time-scales result from changes in chemical conditions, which drive reactions with sediments that favor U(VI) desorption. Grain-scale U(VI) sorption/desorption rates are slow, likely owing to diffusion of U(VI) and other solutes through intra-granular pore domains. In order to improve understanding of the impact of intra-granular diffusion and chemical reactions controlling grain-scale U(VI) release, experiments were conducted on individual particle size fractions of a <8 mm composite of field-contaminated, lower vadose zone sediments. For each size fraction, equilibrium U(VI) sorption/desorption in static batch reactors was well-described by surface complexation models over a range of chemical conditions applicable to the field site. Desorption rates from individual size fractions in flow-through batch reactors, examined under a single set of constant chemical conditions with multiple stop-flow events, were similar for all size fractions <2 mm. Kinetic U(VI) desorption in flow-through batch reactors was modeled using a multi-rate surface complexation approach, where sorption/desorption rates were assumed to be proportional to the displacement from equilibrium and multiple diffusion domains were described with a two-parameter lognormal distribution of mass-transfer rate coefficients. Parameters describing mass transfer were the same for all size fractions <2 mm but differed for the largest (2-8 mm) size fraction. The evolution of pH, along with dissolved cation and carbonate concentrations, was modeled using equilibrium cation exchange, rate-limited calcite dissolution, aerobic respiration, and silica dissolution. Desorption and chemical reaction models calibrated with individual size fractions predicted U(VI) and chemical composition as a function of time for the bulk sediment sample. Volumes of pores less than 2.4 nm, quantified using nitrogen adsorption-desorption isotherms, were the same for all size fractions < 2 mm, nearly double that of the 2-8 mm size fraction. Similarity in the observed pore volumes and multi-rate mass-transfer parameters across all size fractions <2 mm suggest the importance of pores in this size class in controlling slow grain-scale U(VI) desorption rates. Models like these provide a means for testing the influence of grain-scale mass-transfer on the persistence of U(VI) plume at the site.

Size and Charge Dependence of Ion Transport in Human Nail Plate

PubMed Central

Baswan, Sudhir M.; Li, S. Kevin; LaCount, Terri D.; Kasting, Gerald B.

2016-01-01

The electrical properties of human nail plate are poorly characterized, yet are a key determinate of the potential to treat nail diseases such as onychomycosis using iontophoresis. In order to address this deficiency, molar conductivities of 17 electrolytes comprising 12 ionic species were determined in hydrated human nail plate in vitro. Cation transport numbers across the nail for 11 of these electrolytes were determined by the electromotive force method. Effective ionic mobilities and diffusivities at infinite dilution for all ionic species were determined by regression analysis. The ratios of diffusivities in nail to those in solution were found to correlate inversely with the hydrodynamic radii of the ions according to a power law relationship having an exponent of −1.75 ± 0.27, a substantially steeper size dependence than observed for similar experiments in skin. Effective diffusivities of cations in nail were three-fold higher than those of comparably sized anions. These results reflect the strong size and charge selectivity of the nail plate for ionic conduction and diffusion. The analysis implies that efficient transungual iontophoretic delivery of ionized drugs having radii upwards of 5 Å (approximately MW ≥ 340 Da) will require chemical or mechanical alteration of the nail plate. PMID:26886342

Static and transport properties of alkyltrimethylammonium cation-based room-temperature ionic liquids.

PubMed

Seki, Shiro; Tsuzuki, Seiji; Hayamizu, Kikuko; Serizawa, Nobuyuki; Ono, Shimpei; Takei, Katsuhito; Doi, Hiroyuki; Umebayashi, Yasuhiro

2014-05-01

We have measured physicochemical properties of five alkyltrimethylammonium cation-based room-temperature ionic liquids and compared them with those obtained from computational methods. We have found that static properties (density and refractive index) and transport properties (ionic conductivity, self-diffusion coefficient, and viscosity) of these ionic liquids show close relations with the length of the alkyl chain. In particular, static properties obtained by experimental methods exhibit a trend complementary to that by computational methods (refractive index ∝ [polarizability/molar volume]). Moreover, the self-diffusion coefficient obtained by molecular dynamics (MD) simulation was consistent with the data obtained by the pulsed-gradient spin-echo nuclear magnetic resonance technique, which suggests that computational methods can be supplemental tools to predict physicochemical properties of room-temperature ionic liquids.

Ion-Migration Inhibition by the Cation-π Interaction in Perovskite Materials for Efficient and Stable Perovskite Solar Cells.

PubMed

Wei, Dong; Ma, Fusheng; Wang, Rui; Dou, Shangyi; Cui, Peng; Huang, Hao; Ji, Jun; Jia, Endong; Jia, Xiaojie; Sajid, Sajid; Elseman, Ahmed Mourtada; Chu, Lihua; Li, Yingfeng; Jiang, Bing; Qiao, Juan; Yuan, Yongbo; Li, Meicheng

2018-06-25

Migration of ions can lead to photoinduced phase separation, degradation, and current-voltage hysteresis in perovskite solar cells (PSCs), and has become a serious drawback for the organic-inorganic hybrid perovskite materials (OIPs). Here, the inhibition of ion migration is realized by the supramolecular cation-π interaction between aromatic rubrene and organic cations in OIPs. The energy of the cation-π interaction between rubrene and perovskite is found to be as strong as 1.5 eV, which is enough to immobilize the organic cations in OIPs; this will thus will lead to the obvious reduction of defects in perovskite films and outstanding stability in devices. By employing the cation-immobilized OIPs to fabricate perovskite solar cells (PSCs), a champion efficiency of 20.86% and certified efficiency of 20.80% with negligible hysteresis are acquired. In addition, the long-term stability of cation-immobilized PSCs is improved definitely (98% of the initial efficiency after 720 h operation), which is assigned to the inhibition of ionic diffusions in cation-immobilized OIPs. This cation-π interaction between cations and the supramolecular π system enhances the stability and the performance of PSCs efficiently and would be a potential universal approach to get the more stable perovskite devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rotational diffusion of nonpolar and ionic solutes in 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides: is solute rotation always influenced by the length of the alkyl chain on the imidazolium cation?

PubMed

Gangamallaiah, V; Dutt, G B

2012-10-25

In an attempt to find out whether the length of the alkyl chain on the imidazolium cation has a bearing on solute rotation, temperature-dependent fluorescence anisotropies of three structurally similar solutes have been measured in a series of 1-alkyl-3-methylimidazolium (alkyl = methyl, ethyl, propyl, butyl, and hexyl) bis(trifluoromethylsulfonyl)imides. Solute-solvent coupling constants obtained from the experimentally measured reorientation times with the aid of Stokes-Einstein-Debye hydrodynamic theory indicate that there is no influence of the length of the alkyl chain on the rotation of nonpolar, anionic, and cationic solutes 9-phenylanthracene (9-PA), fluorescein (FL), and rhodamine 110 (R110), respectively. It has also been noticed that the rotational diffusion of 9-PA is closer to the predictions of slip hydrodynamics, whereas the rotation of negatively charged FL and positively charged R110 is almost identical and follows stick hydrodynamics in these ionic liquids. Despite having similar shape and size, ionic solutes rotate slower by a factor of 3-4 compared to the nonpolar solute. Interplay of specific and electrostatic interactions between FL and the imidazolium cation of the ionic liquids, and between R110 and the bis(trifluoromethylsulfonyl)imide anion, appear to be responsible for the observed behavior. These results are an indication that the length of the alkyl chain on the imidazolium cation does not alter their physical properties in a manner that has an effect on solute rotation.

Assessing the role of clay authigenesis in the seawater potassium cycle: A paired K and Mg isotope study of deep-sea pore fluids

NASA Astrophysics Data System (ADS)

Santiago Ramos, D. P.; Higgins, J. A.

2017-12-01

In situ formation of clays (clay authigenesis) in marine sediments and altered oceanic crust is an important sink of a number of seawater cations. In particular, clay authigenesis is a major, and yet unconstrained, flux in the global seawater potassium cycle. Potassium is the fourth most abundant cation in the ocean, which constitutes an isotopically enriched K reservoir (δ41K 0‰) compared to the solid Earth (δ41K -0.5‰). Understanding what processes control this isotopic offset is the main goal of this study. Here we use a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS) to measure the K and Mg isotope ratios (41K/39K and 26Mg/24Mg) of deep-sea pore fluids in order to assess the effects of clay formation in the K isotope composition of seawater. Mg isotopes are used as an independent proxy for clay formation, since marine authigenic clays are isotopically distinct from their detrital counterpart, an abundant component of marine sediments. Our study sites (ODP/IODP 1052, U1378, U1395, U1403) vary in location, lithology, age and sedimentation rates; however, pore-fluids from all sites show decreasing K concentrations with depth, suggesting potassium uptake into the sediments. We find that although K concentration trends are similar across all sites, measured δ41K values vary significantly. Results from 1-D diffusion-advection-reaction models suggest that these differences in isotopic profiles arise from a complex interplay between sedimentation rate and K isotopic fractionation during clay formation, aqueous K diffusion and ion exchange reactions. Further, model simulations yield fractionation factors between 0.9980 and 1.0000 for clay formation in deep-sea sediments. Despite the minor contribution of these deep-sea pore-fluids as sinks of seawater K, the processes responsible for K isotope fractionation in our study sites (clay formation and aqueous K diffusion) are also observed at shallow marine systems (major K sinks) and are thus likely responsible for setting the K isotopic composition of seawater.

Polymorphic phase transitions and molecular motion in pyridinium chlorochromate

NASA Astrophysics Data System (ADS)

Pajaķ, Z.; Szafrańska, B.; Czarnecki, P.; Mayer, J.; Kozak, A.

1997-08-01

DTA, DSC, NMR and dielectric studies have been performed for pyridinium chlorochromate over a wide temperature range. A sequence of four solid-solid phase transitions was discovered. The in-plane complex reorientation of the cation is described by a three-well potential model with two correlation times. At higher temperatures one observes simultaneous cation tumbling and diffusion. Thus existence of a new ionic plastic phase is revealed. The domain structure observed suggests ferroelastic properties of the compound.

Predicting Salt Permeability Coefficients in Highly Swollen, Highly Charged Ion Exchange Membranes.

PubMed

Kamcev, Jovan; Paul, Donald R; Manning, Gerald S; Freeman, Benny D

2017-02-01

This study presents a framework for predicting salt permeability coefficients in ion exchange membranes in contact with an aqueous salt solution. The model, based on the solution-diffusion mechanism, was tested using experimental salt permeability data for a series of commercial ion exchange membranes. Equilibrium salt partition coefficients were calculated using a thermodynamic framework (i.e., Donnan theory), incorporating Manning's counterion condensation theory to calculate ion activity coefficients in the membrane phase and the Pitzer model to calculate ion activity coefficients in the solution phase. The model predicted NaCl partition coefficients in a cation exchange membrane and two anion exchange membranes, as well as MgCl 2 partition coefficients in a cation exchange membrane, remarkably well at higher external salt concentrations (>0.1 M) and reasonably well at lower external salt concentrations (<0.1 M) with no adjustable parameters. Membrane ion diffusion coefficients were calculated using a combination of the Mackie and Meares model, which assumes ion diffusion in water-swollen polymers is affected by a tortuosity factor, and a model developed by Manning to account for electrostatic effects. Agreement between experimental and predicted salt diffusion coefficients was good with no adjustable parameters. Calculated salt partition and diffusion coefficients were combined within the framework of the solution-diffusion model to predict salt permeability coefficients. Agreement between model and experimental data was remarkably good. Additionally, a simplified version of the model was used to elucidate connections between membrane structure (e.g., fixed charge group concentration) and salt transport properties.

Transition metal impurities in the solid electrolyte LLZO (Li7La3Zr2O12) : Transport rates and their impact on Li-ion mobility

NASA Astrophysics Data System (ADS)

Yang, Sheng; Siegel, Donald

LLZO has many properties of an ideal solid electrolyte in lithium-ion batteries since it could enable the use of high voltage electrodes and hence enhance the energy density of lithium ion batteries. With supervalent cation doping such as Al3+, Ga3+ on the Li-site, the room temperature ionic conductivity of the cubic LLZO can accomplish high ionic conductivity up to 1mS/cm. However, some experiments suggest that mutual diffusion layers were formed between LLZO and cathode where transition metal (TM) diffused into LLZO, which could possibly lead to large interfacial resistance. In this study, we quantified the performance of LLZO after doping with cobalt, manganese, iron and nickel. In particular, we used molecular dynamics simulations with empirical Morse-type potentials to investigate the TM transport rates and their impact on Li-ion mobility. Our work indicates that TM impurities diffuse slower than Li-ion and they will result in a decrease in the Li-ion mobility by blocking Li-ion pathways. Our work shines light on the origin of interfacial resistance between LLZO and different cathodes. This work was supported by U.S. Department Energy's U.S.- China Clean Energy Research Center Clean Vehicles Consortium (CERC CVC), Grant No. DE-PI0000012.

Contrasting the Influence of Cationic Amino Acids on the Viscosity and Stability of a Highly Concentrated Monoclonal Antibody.

PubMed

Dear, Barton J; Hung, Jessica J; Truskett, Thomas M; Johnston, Keith P

2017-01-01

To explain the effects of cationic amino acids and other co-solutes on the viscosity, stability and protein-protein interactions (PPI) of highly concentrated (≥200 mg/ml) monoclonal antibody (mAb) solutions to advance subcutaneous injection. The viscosities of ≥200 mg/ml mAb1 solutions with various co-solutes and pH were measured by capillary rheometry in some cases up to 70,000 s -1 . The viscosities are analyzed in terms of dilute PPI characterized by diffusion interaction parameters (k D ) from dynamic light scattering (DLS). MAb stability was measured by turbidity and size exclusion chromatography (SEC) after 4 weeks of 40°C storage. Viscosity reductions were achieved by reducing the pH, or adding histidine, arginine, imidazole or camphorsulfonic acid, each of which contains a hydrophobic moiety. The addition of inorganic electrolytes or neutral osmolytes only weakly affected viscosity. Systems with reduced viscosities also tended to be Newtonian, while more viscous systems were shear thinning. Viscosity reduction down to 20 cP at 220 mg/ml mAb1 was achieved with co-solutes that are both charged and contain a hydrophobic interaction domain for sufficient binding to the protein surface. These reductions are related to the DLS diffusion interaction parameter, k D , only after normalization to remove the effect of charge screening. Shear rate profiles demonstrate that select co-solutes reduce protein network formation.

Electronic absorption spectra of hydrogenated protonated naphthalene and proflavine

NASA Astrophysics Data System (ADS)

Bonaca, A.; Bilalbegović, G.

2011-09-01

We study hydrogenated cations of two polycyclic hydrocarbon molecules as models of hydrogenated organic species that form in the interstellar medium. Optical spectra of the hydrogenated naphthalene cation Hn-C10H+8 for n= 1, 2 and 10, as well as the astrobiologically interesting hydrogenated proflavine cation Hn-C13H11N+3 for n= 1 and 14, are calculated. The pseudopotential time-dependent density functional theory is used. It is found that the fully hydrogenated proflavine cation H14-C13H11N+3 shows a broad spectrum in which the positions of individual lines are almost lost. The positions, shapes and intensities of lines change in hydronaphthalene and hydroproflavine cations, showing that hydrogen additions induce substantially different optical spectra in comparison with base polycyclic hydrocarbon cations. One calculated line in the visible spectrum of H10-C10H+8 and one in the visible spectrum of H-C13H11N+3 are close to the measured diffuse interstellar bands. We also present the positions of near-ultraviolet lines.

Polarizability effects on the structure and dynamics of ionic liquids

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

Cavalcante, Ary de Oliveira, E-mail: arycavalcante@ufam.edu.br; Departamento de Química, Universidade Federal do Amazonas, Av. Rodrigo Octávio, 6200, Coroado, Manaus, AM; Ribeiro, Mauro C. C.

2014-04-14

Polarization effects on the structure and dynamics of ionic liquids are investigated using molecular dynamics simulations. Four different ionic liquids were simulated, formed by the anions Cl{sup −} and PF{sub 6}{sup −}, treated as single fixed charge sites, and the 1-n-alkyl-3-methylimidazolium cations (1-ethyl and 1-butyl-), which are polarizable. The partial charge fluctuation of the cations is provided by the electronegativity equalization model (EEM) and a complete parameter set for the cations electronegativity (χ) and hardness (J) is presented. Results obtained from a non-polarizable model for the cations are also reported for comparison. Relative to the fixed charged model, the equilibriummore » structure of the first solvation shell around the imidazolium cations shows that inclusion of EEM polarization forces brings cations closer to each other and that anions are preferentially distributed above and below the plane of the imidazolium ring. The polarizable model yields faster translational and reorientational dynamics than the fixed charges model in the rotational-diffusion regime. In this sense, the polarizable model dynamics is in better agreement with the experimental data.« less

LiBi{sub 3}S{sub 5}—A lithium bismuth sulfide with strong cation disorder

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

Nakhal, Suliman; Wiedemann, Dennis, E-mail: dennis.wiedemann@chem.tu-berlin.de; Stanje, Bernhard

Among chalcogenide semiconductors for thermoelectric applications, alkali-metal bismuth compounds occur in many complex compositions favorable for high performance. Although LiBi{sub 3}S{sub 5} had been announced in 1977, the potential 1D lithium-ion conductor has hitherto eluded selective synthesis and structure determination. In this study, we present a solid-state route to phase-pure LiBi{sub 3}S{sub 5} powder starting from LiBiS{sub 2} and Bi{sub 2}S{sub 3}. Neutron diffractograms and lithium NMR spectra reveal its crystal structure to be a cation-disordered variety of the AgBi{sub 3}S{sub 5} type (synthetic pavonite; monoclinic, C2/m). Topological analyses and lithium NMR relaxometry suggest that correlated lithium-ion diffusion with activationmore » energies up to 0.66(2) eV occurs along the channels in b direction including tetrahedral voids. Because of cation disorder, immobile bismuth(III) ions clog these pathways, making LiBi{sub 3}S{sub 5} a moderate to poor ionic conductor. The synthesis route reported is nonetheless promising for new lithium bismuth sulfides with, possibly ordered, structure types of the pavonite homologous series. - Graphical abstract: Phase-pure LiBi{sub 3}S{sub 5} has been synthesized and shown to crystallize in cation-disordered variety of the AgBi{sub 3}S{sub 5} type (synthetic pavonite, C2/m) using neutron diffractometry. Topological analyses and NMR relaxometry suggest that immobile Bi{sup 3+} ions clog migration channels along b, making the material a poor lithium conductor. Display Omitted - Highlights: • Phase-pure LiBi{sub 3}S{sub 5} has been synthesized using a promising solid-state route. • LiBi{sub 3}S{sub 5} crystallizes in a cation-disordered variant of the AgBi{sub 3}S{sub 5} type. • Topological analyses suggest lithium diffusion in channels along b. • NMR relaxometry finds activation energies of diffusion as high as 0.66(2) eV. • Because of disorder, LiBi{sub 3}S{sub 5} is a moderate to poor lithium-ion conductor.« less

Li Storage of Calcium Niobates for Lithium Ion Batteries.

PubMed

Yim, Haena; Yu, Seung-Ho; Yoo, So Yeon; Sung, Yung-Eun; Choi, Ji-Won

2015-10-01

New types of niobates negative electrode were studied for using in lithium-ion batteries in order to alternate metallic lithium anodes. The potassium intercalated compound KCa2Nb3O10 and proton intercalated compound HCa2Nb3O10 were studied, and the electrochemical results showed a reversible cyclic voltammetry profile with acceptable discharge capacity. The as-prepared KCa2Nb3O10 negative electrode had a low discharge capacity caused by high overpotential, but the reversible intercalation and deintercalation reaction of lithium ions was activated after exchanging H+ ions for intercalated K+ ions. The initial discharge capacity of HCa2Nb3O10 was 54.2 mAh/g with 92.1% of coulombic efficiency, compared with 10.4 mAh/g with 70.2% of coulombic efficiency for KCa2Nb3O10 at 1 C rate. The improved electrochemical performance of the HCa2Nb3O10 was related to the lower bonding energy between proton cation and perovskite layer, which facilitate Li+ ions intercalating into the cation site, unlike potassium cation and perovskite layer. Also, this negative material can be easily exfoliated to Ca2Nb3O10 layer by using cation exchange process. Then, obtained two-dimensional nanosheets layer, which recently expected to be an advanced electrode material because of its flexibility, chemical stable, and thin film fabricable, can allow Li+ ions to diffuse between the each perovskite layer. Therefore, this new type layered perovskite niobates can be used not only bulk-type lithium ion batteries but also thin film batteries as a negative material.

Variable Temperature Infrared Spectroscopy Investigation of Benzoic Acid Interactions with Montmorillonite Clay Interlayer Water.

PubMed

Nickels, Tara M; Ingram, Audrey L; Maraoulaite, Dalia K; White, Robert L

2015-07-01

Molecular interactions between benzoic acid and cations and water contained in montmorillonite clay interlayer spaces are characterized by using variable temperature diffuse reflection infrared Fourier transform spectroscopy (VT-DRIFTS). Using sample perturbation and difference spectroscopy, infrared spectral changes resulting from removal of interlayer water and associated changes in local benzoic acid environments are identified. Difference spectra features can be correlated with changes in specific molecular vibrations that are characteristic of benzoic acid molecular orientation. Results suggest that the carboxylic acid functionality of benzoic acid interacts with interlayer cations through a bridging water molecule and that this interaction is affected by the nature of the cation present in the clay interlayer space.

Methods and apparatus for using gas and liquid phase cathodic depolarizers

NASA Technical Reports Server (NTRS)

Murphy, Oliver J. (Inventor); Hitchens, G. Duncan (Inventor)

1998-01-01

The invention provides methods for using gas and liquid phase cathodic depolarizers in an electrochemical cell having a cation exchange membrane in intimate contact with the anode and cathode. The electrochemical conversion of cathodic depolarizers at the cathode lowers the cell potential necessary to achieve a desired electrochemical conversion, such as ozone evolution, at the anode. When gaseous cathodic depolarizers, such as oxygen, are used, a gas diffusion cathode having the cation exchange membrane bonded thereto is preferred. When liquid phase cathodic depolarizers are used, the cathode may be a flow-by electrode, flow-through electrode, packed-bed electrode or a fluidized-bed electrode in intimate contact with the cation exchange membrane.

Water vapor diffusion membrane development. [for water recovery purposes onboard manned spacecraft

NASA Technical Reports Server (NTRS)

Tan, M. K.

1974-01-01

The phase separator component used as a membrane in the vapor diffusion process (VRD) for the recovery of potable water from urine on manned space missions of extended duration was investigated, with particular emphasis on cation-selective membranes because of their noted mechanical strength, superior resistance to acids, oxidants, and germicides, and their potential resistance to organic foulants. Two of the membranes were tested for 700 hours continuously, and were selected on the basis of criteria deemed important to an effective water reclamation system onboard spacecraft. The samples of urine were successfully processed by removing 93 percent of their water content in 70 hours using the selected membranes. Pretreatment with an acid-oxidant formulation improved product quality. Cation exchange membranes were shown to possess superior mechanical strength and chemical resistance, as compared to cellulosic membranes.

Biphasic interactions between a cationic dendrimer and actin.

PubMed

Ruenraroengsak, Pakatip; Florence, Alexander T

2010-12-01

Gene delivery systems face the problem not only of the route toward the cell and tissues in question, but also of the molecularly crowded environment of both the cytoplasm and the nucleus itself. One of the physical barriers in the cytoplasm for diffusing nanoparticles is an actin network. Here, we describe the finding that a self-fluorescent sixth generation cationic dendrimer (6 nm in diameter) interacts reversibly and possibly electrostatically with actin filaments in vitro. Not only does this interaction slow the diffusion of the dendrimer but it also affects actin polymerization in a biphasic manner. At low concentrations the dendrimer behaves like a G-binding actin protein, retarding actin polymerization, whereas at high concentrations the dendrimer acts as a nucleating protein accelerating the polymerization. Thus in vivo the diffusion of a dendrimer carrier such as this has both physical and chemical elements: by decreasing polymerization it might accelerate its own transport, and by enhancing actin polymerization retard it. This finding suggests that such a dendrimer may have a role as an anticancer agent through its inhibitory effect on actin polymerization.

Corrosion characteristics of Ni-base superalloys in high temperature steam with and without hydrogen

NASA Astrophysics Data System (ADS)

Kim, Donghoon; Kim, Daejong; Lee, Ho Jung; Jang, Changheui; Yoon, Duk Joo

2013-10-01

The hot steam corrosion behavior of Alloy 617 and Haynes 230 were evaluated in corrosion tests performed at 900 °C in steam and steam + 20 vol.% H2 environments. Corrosion rates of Alloy 617 was faster than that of Haynes 230 at 900 °C in steam and steam + 20 vol.% H2 environments. When hydrogen was added to steam, the corrosion rate was accelerated because added hydrogen increased the concentration of Cr interstitial defects in the oxide layer. Isolated nodular MnTiO3 oxides were formed on the MnCr2O4/Cr2O3 oxide layer and sub-layer Cr2O3 was formed in steam and steam + 20 vol.% H2 for Alloy 617. On the other hand, a MnCr2O4 layer was formed on top of the Cr2O3 oxide layer for Haynes 230. The extensive sub-layer Cr2O3 formation resulted from the oxygen or hydroxide inward diffusion in such environments. When hydrogen was added, the initial surface oxide morphology was changed from a convex shape to platelets because of the accelerated diffusion of cations under the oxide layer.

Characterization of new polymer-grafted protein cation exchangers developed by partial neutralization of carboxyl groups derivatized by modification of poly(ethylenimine)-Sepharose with succinic anhydride.

PubMed

Zhao, Yangyang; Dong, Xiaoyan; Yu, Linling; Liu, Yang; Sun, Yan

2018-05-18

Previously, we have studied protein adsorption and chromatographic behaviors on poly(ethylenimine) (PEI)-grafted Sepharose FF anion-exchange resins, and found that protein uptake rates increased greatly when PEI grafting density reached over a critical ionic capacity (cIC) due to the occurrence of the "chain delivery" effect. Moreover, by partial charge neutralization of starting resin FF-PEI-L740 (IC = 740 mmol/L, larger than the cIC) with sodium acetate to FF-PEI-R440, it exhibited a three-fold increase in uptake rate over FF-PEI-L740. In this work, to take the advantages of PEI and extend the applications of the PEI-grafted resins in cation-exchange chromatography, a series of cation exchangers of five different ICs were developed. First, the charged of FF-PEI-L740 was reversed from positive to negative by reaction with excess succinic anhydride, which created a cation-exchanger with an IC of 970 mmol/L (FF-FEI-C970). FF-PEI-C970 was further modified with ethanolamine for partial charge neutralizations, leading to the preparation of four charge-reduced cation exchangers with IC values (in mmol/L) of 780, 630, 560 and 430, which were denoted as FF-PEI-CR780, -CR630 -CR560 and -CR430, respectively. Protein adsorption and chromatographic behaviors were investigated using lysozyme (Lys) as the model protein. It was found that, the resins of high and moderate IC values (IC ≥ 560 mmol/L) afforded adsorption capacities up to over 230 mg/mL. Besides, the uptake rate, represented by the effective pore diffusivity (D e/ D 0 ), exhibited significant increase from 0.067 (FF-PEI-C970 and FF-PEI-CR780) to 0.343 (FF-PEI-CR630 and FF-PEI-CR560) and then to 1.035 (FF-PEI-CR430) with decreasing IC. It was considered that decreasing IC led to the decreased protein binding sites (binding strength), which encouraged the occurrence of the "chain delivery" effect. Moreover, the resins of high and moderate IC values, particularly, the resins of moderate IC values (FF-PEI-CR630 and FF-PEI-CR560), presented both high adsorption capacities and uptake kinetics at 0-100 mmol/L NaCl. Besides, dynamic binding capacity achieved 150 mg/mL for the resins of moderate IC values at 0 mmol/L NaCl concentration, and afforded >110 mg/mL for the resin of high IC values at 0-100 mmol/L NaCl concentration. The results proved the excellent IEC performance of the PEI-derived cation exchangers. Copyright © 2018 Elsevier B.V. All rights reserved.

Cation Diffusion in Plagioclase Feldspar

NASA Astrophysics Data System (ADS)

Morse, S. A.

1984-08-01

Steep compositional gradients in igneous plagioclase feldspar from slowly cooled intrusive bodies imply a maximum value of the intracrystalline diffusion coefficient for NaSi leftrightarrows CaAl exchange, Dmax~ 10-20 centimeters squared per second for temperatures in the range 1250 degrees to 1000 degrees C. Millimeter-sized grains cannot be homogenized in all geologic time; hence reactive equilibrium crystallization of plagioclase from the melt does not occur in dry systems.

Size and Charge Dependence of Ion Transport in Human Nail Plate.

PubMed

Baswan, Sudhir M; Li, S Kevin; LaCount, Terri D; Kasting, Gerald B

2016-03-01

The electrical properties of human nail plate are poorly characterized yet are a key determinate of the potential to treat nail diseases, such as onychomycosis, using iontophoresis. To address this deficiency, molar conductivities of 17 electrolytes comprising 12 ionic species were determined in hydrated human nail plate in vitro. Cation transport numbers across the nail for 11 of these electrolytes were determined by the electromotive force method. Effective ionic mobilities and diffusivities at infinite dilution for all ionic species were determined by regression analysis. The ratios of diffusivities in nail to those in solution were found to correlate inversely with the hydrodynamic radii of the ions according to a power law relationship having an exponent of -1.75 ± 0.27, a substantially steeper size dependence than observed for similar experiments in skin. Effective diffusivities of cations in nail were 3-fold higher than those of comparably sized anions. These results reflect the strong size and charge selectivity of the nail plate for ionic conduction and diffusion. The analysis implies that efficient transungual iontophoretic delivery of ionized drugs having radii upward of 5 Å (molecular weight, ca. ≥ 340 Da) will require chemical or mechanical alteration of the nail plate. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Sticky when wet

NASA Astrophysics Data System (ADS)

Chen, Ji; Michaelides, Angelos

2018-03-01

The aqueous hydronium cation diffuses about twice as fast as the aqueous hydroxide anion in liquid water, but the origin of this behaviour has been unclear. Now, state-of-the-art simulations provide an explanation for this long-standing conundrum.

Extrinsic Cation Selectivity of 2D Membranes

PubMed Central

2017-01-01

From a systematic study of the concentration driven diffusion of positive and negative ions across porous 2D membranes of graphene and hexagonal boron nitride (h-BN), we prove their cation selectivity. Using the current–voltage characteristics of graphene and h-BN monolayers separating reservoirs of different salt concentrations, we calculate the reversal potential as a measure of selectivity. We tune the Debye screening length by exchanging the salt concentrations and demonstrate that negative surface charge gives rise to cation selectivity. Surprisingly, h-BN and graphene membranes show similar characteristics, strongly suggesting a common origin of selectivity in aqueous solvents. For the first time, we demonstrate that the cation flux can be increased by using ozone to create additional pores in graphene while maintaining excellent selectivity. We discuss opportunities to exploit our scalable method to use 2D membranes for applications including osmotic power conversion. PMID:28157333

Supramolecular architecture based on [Fe(CN)6]3- metallotectons and melaminium synthons

NASA Astrophysics Data System (ADS)

Krichen, Firas; Walha, Siwar; Lhoste, Jérôme; Bulou, Alain; Kabadou, Ahlem; Goutenoire, François

2017-10-01

Assembly involving [Fe(CN)6]3- metallotectons as building units and melaminium organic cation has been envisioned in order to elaborate a hybrid supramolecular based on ionic H-bonds with formula {(H-mel)4[Fe(CN)6]Cl} (H-mel+: melaminium cation). The compound has been prepared by diffusion method and characterized by single-crystal X-ray diffraction, EDX analysis, and Raman-IR spectroscopies with assignment from ab initio calculations. The melaminium exhibit self cationic coupling with cyclic hydrogen bonds to give a one dimensional {[H-mel]+}∝ synthon. Therefore, these cationic ribbons are inter-linked via hydrogen bonds by the anionic tectons [Fe(CN)6]3- and chlorine anion resulting on a 3D network. Molecular hirshfeld surfaces revealed that the crystal structure has been supported mainly by Nsbnd H⋯N and Nsbnd H⋯Cl intermolecular Hydrogen bonds and by favoured C⋯C and C⋯N weak interactions.

[Effects of sub-micro emulsion composition on cellular disposition of incorporated lipophilic drug].

PubMed

Sun, Xiao-Yi; Xiang, Zhi-Qiang; Wu, Shuo; Lv, Yuan-Yuan; Liang, Wen-Quan

2013-09-01

To investigate the effects of sub-micro emulsion composition on cellular uptake and disposition of incorporated lipophilic drug. Sub-micro emulsions containing 10 % oil, 1.2 % lecithin and 2.25 % glycerol were prepared, and the fluorescent agent coumarin 6 was used as a model drug. The effects of oil types, co-surfactants and cationic lipid on uptake and elimination kinetics of 6-coumarin in HeLa cells were studied. The uptake mechanism of sub-micro emulsions was further investigated. Oil type and Tweens had no influence on the cellular uptake. Modifications of surfactants with Span series increased the cellular influx, among which Span 20 with hydrophilic-lipophilic balance (HLB) value of 8.6 was the best enhancer. The intracellular drug level reached up to (46.09 ± 1.98)ng/μg protein which had significant difference with control group [(38.54 ± 0.34)ng/μg protein]. The positively charged emulsions significantly increased the uptake rate constant and elimination rate constant which were 4 times and 1.5 times of those in anionic groups, respectively. The uptake enhancement was also observed in cationic emulsions, cellular concentrations at plateau were (42.73 ± 0.84)ng/μg protein, which was about 3 times of that in anionic emulsions [(15.71 ± 0.74)ng/μg protein], when extracellular drug concentration kept at 100 ng/ml. Cationic emulsions delivered the payload mainly by direct drug transfer to contacted cells, while the negative ones depended on both drug passive diffusion and clathrin-mediated endocytosis of drug containing oil droplets which accounted for 20% of the intracellular drug. Interfacial characteristic of sub-micro emulsions such as co-surfactants HLB as well as zeta potentials can influence lipophilic drug both in cellular uptake and elimination.

One-pot template-free synthesis of monodisperse hollow hydrogel microspheres and their resulting properties.

PubMed

Lim, Hyung-Seok; Kwon, Eunji; Lee, Moonjoo; Moo Lee, Young; Suh, Kyung-Do

2013-08-01

Monodisperse poly(methacrylic acid/ethyleneglycoldimethacrylate) (MAA/EGDMA) hollow microcapsules, which exhibit pH-responsive behavior, are prepared by diffusion of cationic surfactants and hydrophobic interaction. During the association of the negatively charged hydrogel microspheres and an oppositely charged surfactant (cetyltrimethylammonium bromide, CTA(+)B), the hydrophobic polymer-surfactant complexes that form are separated from the internal water; consequently, a hollow structure can be formed. Confocal laser scanning microscopy, UV spectro-scopy and zeta potential are employed to study the formation of the hollow structure during the diffusion of the cationic surfactant. The controlled release behavior of methylene blue as a model drug from the as-prepared poly(MAA/EGDMA) microcapsules with a hollow structure is investigated under different pH conditions. The hollow structure can be retained, even during repetitive pH changes. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The ultraviolet and visible spectrum of the polycyclic aromatic hydrocarbon C10H8(+) - Possible contributions to the diffuse interstellar bands and to the ultraviolet-visible extinction

NASA Technical Reports Server (NTRS)

Salama, F.; Allamandola, L. J.

1992-01-01

The properties of the cation of the PAH naphthalene (C10H8(+)) isolated in inert gas matrices under conditions relevant to astrophysical environments are described. The band at 6741 A is the strongest and falls close to the weak 6742 A diffuse interstellar bands (DIBs). Five other weaker bands also fall remarkably close to the positions of known DIBs. A very intense and broad continuum extended from the UV to the visible, which seems to be associated with the ion, is reported. The molar absorption coefficient at the peak of the continuum is 2.0 x 10 exp 6 cu dm/mol cm. If a continuum is a general property of PAH cations, this characteristic will have a strong impact on the understanding of how PAHs convert interstellar UV and visible radiation into IR radiation.

Effect of the pore water composition on the diffusive anion transport in argillaceous, low permeability sedimentary rocks

NASA Astrophysics Data System (ADS)

Wigger, Cornelia; Van Loon, Luc R.

2018-06-01

The effect of the pore water composition on the diffusive anion transport was studied for two different argillaceous, low permeability sedimentary rocks, Opalinus Clay (OPA) and Helvetic Marl (HM). The samples were saturated with different solutions with varying molar concentration and different main cations in the solution: NaCl based pore solutions and CaCl2 based pore solutions. The total porosity was measured by through-diffusion experiments with the neutral tracer HTO. Experiments performed in NaCl solutions resulted in a porosity of 0.12 for OPA and 0.03 for HM, and are consistent with results of the experiments in CaCl2 solutions. The total porosity was independent of the molar concentration, in contrast to the measured anion porosity, which increased with increasing molar concentration. It could further be observed that the pore solution based on the bivalent cation calcium shielded the negative surface charge stronger than the monovalent cation sodium, resulting in a larger measureable anion-accessible porosity in the case of CaCl2 solutions. The data was modelled based on an adapted Donnan approach of Birgersson and Karnland (2009). The model had to be adjusted with a permanent free, uncharged porosity, as well as with structural information on the permanent anion exclusion because of so-called bottleneck pores. Both parameters can only be evaluated from experiments. Nevertheless, taking these two adaptions into account, the effect of varying pore water compositions on the anion-accessible porosity of the investigated argillaceous rocks could be satisfactorily described.

Driving mechanisms of ionic polymer actuators having electric double layer capacitor structures.

PubMed

Imaizumi, Satoru; Kato, Yuichi; Kokubo, Hisashi; Watanabe, Masayoshi

2012-04-26

Two solid polymer electrolytes, composed of a polyether-segmented polyurethaneurea (PEUU) and either a lithium salt (lithium bis(trifluoromethanesulfonyl)amide: Li[NTf2]) or a nonvolatile ionic liquid (1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide: [C2mim][NTf2]), were prepared in order to utilize them as ionic polymer actuators. These salts were preferentially dissolved in the polyether phases. The ionic transport mechanism of the polyethers was discussed in terms of the diffusion coefficients and ionic transference numbers of the incorporated ions, which were estimated by means of pulsed-field gradient spin-echo (PGSE) NMR. There was a distinct difference in the ionic transport properties of each polymer electrolyte owing to the difference in the magnitude of interactions between the cations and the polyether. The anionic diffusion coefficient was much faster than that of the cation in the polyether/Li[NTf2] electrolyte, whereas the cation diffused faster than the anion in the polyether/[C2mim][NTf2] electrolyte. Ionic polymer actuators, which have a solid-state electric-double-layer-capacitor (EDLC) structure, were prepared using these polymer electrolyte membranes and ubiquitous carbon materials such as activated carbon and acetylene black. On the basis of the difference in the motional direction of each actuator against applied voltages, a simple model of the actuation mechanisms was proposed by taking the difference in ionic transport properties into consideration. This model discriminated the behavior of the actuators in terms of the products of transference numbers and ionic volumes. The experimentally observed behavior of the actuators was successfully explained by this model.

First principles molecular dynamics of molten NaI: Structure, self-diffusion, polarization effects, and charge transfer

NASA Astrophysics Data System (ADS)

Galamba, N.; Costa Cabral, B. J.

2007-09-01

The structure and self-diffusion of NaI and NaCl at temperatures close to their melting points are studied by first principles Hellmann-Feynman molecular dynamics (HFMD). The results are compared with classical MD using rigid-ion (RI) and shell-model (ShM) interionic potentials. HFMD for NaCl was reported before at a higher temperature [N. Galamba and B. J. Costa Cabral, J. Chem. Phys. 126, 124502 (2007)]. The main differences between the structures predicted by HFMD and RI MD for NaI concern the cation-cation and the anion-cation pair correlation functions. A ShM which allows only for the polarization of I- reproduces the main features of the HFMD structure of NaI. The inclusion of polarization effects for both ionic species leads to a more structured ionic liquid, although a good agreement with HFMD is also observed. HFMD Green-Kubo self-diffusion coefficients are larger than those obtained from RI and ShM simulations. A qualitative study of charge transfer in molten NaI and NaCl was also carried out with the Hirshfeld charge partitioning method. Charge transfer in molten NaI is comparable to that in NaCl, and results for NaCl at two temperatures support the view that the magnitude of charge transfer is weakly state dependent for ionic systems. Finally, Hirshfeld charge distributions indicate that differences between RI and HFMD results are mainly related to polarization effects, while the influence of charge transfer fluctuations is minimal for these systems.

Effect of the pore water composition on the diffusive anion transport in argillaceous, low permeability sedimentary rocks.

PubMed

Wigger, Cornelia; Van Loon, Luc R

2018-06-01

The effect of the pore water composition on the diffusive anion transport was studied for two different argillaceous, low permeability sedimentary rocks, Opalinus Clay (OPA) and Helvetic Marl (HM). The samples were saturated with different solutions with varying molar concentration and different main cations in the solution: NaCl based pore solutions and CaCl 2 based pore solutions. The total porosity was measured by through-diffusion experiments with the neutral tracer HTO. Experiments performed in NaCl solutions resulted in a porosity of 0.12 for OPA and 0.03 for HM, and are consistent with results of the experiments in CaCl 2 solutions. The total porosity was independent of the molar concentration, in contrast to the measured anion porosity, which increased with increasing molar concentration. It could further be observed that the pore solution based on the bivalent cation calcium shielded the negative surface charge stronger than the monovalent cation sodium, resulting in a larger measureable anion-accessible porosity in the case of CaCl 2 solutions. The data was modelled based on an adapted Donnan approach of Birgersson and Karnland (2009). The model had to be adjusted with a permanent free, uncharged porosity, as well as with structural information on the permanent anion exclusion because of so-called bottleneck pores. Both parameters can only be evaluated from experiments. Nevertheless, taking these two adaptions into account, the effect of varying pore water compositions on the anion-accessible porosity of the investigated argillaceous rocks could be satisfactorily described. Copyright © 2018 Elsevier B.V. All rights reserved.

Quenching mechanisms and diffusional pathways in micellar systems unravelled by time-resolved magnetic-field effects.

PubMed

Goez, Martin; Henbest, Kevin B; Windham, Emma G; Maeda, Kiminori; Timmel, Christiane R

2009-06-08

Magnetic-field effects (MFEs) are used to investigate the photoreaction of xanthone (A) and DABCO (D) in anionic (SDS) or cationic (DTAC) micelles at high pH (DABCO = 1,4-diazabicyclo[2.2.2]octane, SDS = sodium dodecyl sulfate, DTAC = dodecyl trimethyl ammonium chloride). From MFE experiments with nanosecond time resolution, the radical anion A(.)(-) can be observed without any interference from the much more strongly absorbing triplet (3)A*, the different quenching processes can be separated and their rates can be measured. Triplet (3)A* is quenched dynamically both by the SDS micelle (k(1) = 5.0x10(5) s(-1)) and by DABCO approaching from the aqueous phase (k(2) = 2.0x10(9) M(-1) s(-1)). Static quenching by solubilised DABCO (association constant with the SDS micelles, 1.5 M(-1)) also participates at high DABCO concentrations, but is chemically nonproductive and does not lead to MFE generation. The MFEs stemming from the radical ion pairs A(.)(-) D(.)(+) are about 40 times larger in the anionic micelles than in the cationic ones despite a higher yield of free radicals in the latter case. This can be rationalised by different diffusional dynamics: Because of the location of their precursors, A(.)(-) and D(.)(+) are formed at opposite sides of the micelle boundary. Subsequently, the negatively charged Stern layer of the SDS micelle traps the radical cation, which then undergoes surface diffusion, so both the recombination probability and the spin mixing are high; in contrast, the positive surface charge of the DTAC micelle forces the radical cation into the bulk of the solution, thus efficiently blocking a recombination.

Adsorption of pharmaceuticals onto trimethylsilylated mesoporous SBA-15.

PubMed

Bui, Tung Xuan; Pham, Viet Hung; Le, Son Thanh; Choi, Heechul

2013-06-15

The adsorption of a complex mixture of 12 selected pharmaceuticals to trimethylsilylated mesoporous SBA-15 (TMS-SBA-15) has been investigated by batch adsorption experiments. The adsorption of pharmaceuticals to TMS-SBA-15 was highly dependent on the solution pH and pharmaceutical properties (i.e., hydrophobicity (logKow) and acidity (pKa)). Good log-log linear relationships between the adsorption (Kd) and pH-dependent octanol-water coefficients (Kow(pH)) were then established among the neutral, anionic, and cationic compounds, suggesting hydrophobic interaction as a primary driving force in the adsorption. In addition, the neutral species of each compound accounted for a major contribution to the overall compound adsorption onto TMS-SBA-15. The adsorption kinetics of pharmaceuticals was evaluated by the nonlinear first-order and pseudo-second-order models. The first-order model gave a better fit for five pharmaceuticals with lower adsorption capacity, whereas the pseudo-second-order model fitted better for seven pharmaceuticals having higher adsorption capacity. In the same group of properties, pharmaceuticals having higher adsorption capacity exhibited faster adsorption rates. The rate-limiting steps for adsorption of pharmaceuticals onto TMS-SBA-15 are boundary layer diffusion and intraparticle diffusion including diffusion in mesopores and micropores. In addition, the adsorption of pharmaceuticals to TMS-SBA-15 was not influenced by the change of initial pharmaceutical concentration (10-100μgL(-1)) and the presence of natural organic matter. Copyright © 2013 Elsevier B.V. All rights reserved.

Transport of K+ and other cations across phospholipid membranes by nonesterified fatty acids.

PubMed

Sharpe, M A; Cooper, C E; Wrigglesworth, J M

1994-07-01

The rate of change of internal pH and transmembrane potential has been monitored in liposomes following the external addition of various cation salts. Oleic acid increases the transmembrane movement of H+ following the imposition of a K+ gradient. An initial fast change in internal pH is seen followed by a slower rate of alkalinization. High concentrations of the fatty acid enhance the rate comparable to that seen in the presence of nigericin in contrast to the effect of FCCP (carbonyl cyanide p-(tri-fluoromethoxy)phenyl hydrazone) which saturates at an intermediate value. The ability of nonesterified fatty acids to catalyze the movement of cations across the liposome membrane increases with the degree of unsaturation and decreases with increasing chain length. Li and Na salts cause a similar initial fast pH change but have less effect on the subsequent slower rate. Similarly, the main effect of divalent cation salts is on the initial fast change. The membrane potential can enhance or inhibit cation transport depending on its polarity with respect to the cation gradient. It is concluded that nonesterified fatty acids have the capability to complex with, and transport, a variety of cations across phospholipid bilayers. However, they do not act simply as proton/cation exchangers analogous to nigericin nor as protonophores analogous to FCCP. The full cycle of ionophoric action involves a combination of both functions.

On two alternative mechanisms of ethane activation over ZSM-5 zeolite modified by Zn2+ and Ga1+ cations.

PubMed

Kazansky, V B; Subbotina, I R; Rane, N; van Santen, R A; Hensen, E J M

2005-08-21

The activation of ethane over zinc- and gallium-modified HZSM-5 dehydrogenation catalysts was studied by diffuse reflectance infrared spectroscopy. Hydrocarbon activation on HZSM-5 modified by bivalent Zn and univalent Ga cations proceeds via two distinctly different mechanisms. The stronger molecular adsorption of ethane by the acid-base pairs formed by distantly separated cationic Zn2+ and basic oxygen sites results already at room temperature in strong polarizability of adsorbed ethane and subsequent heterolytic dissociative adsorption at moderate temperatures. In contrast, molecular adsorption of ethane on Ga+ cations is weak. At high temperatures dissociative hydrocarbon adsorption takes place, resulting in the formation of ethyl and hydride fragments coordinating to the cationic gallium species. Whereas in the zinc case a Brønsted acid proton is formed upon ethane dissociation, decomposition of the ethyl fragment on gallium results in gallium dihydride species and does not lead to Brønsted acid protons. This difference in alkane activation has direct consequences for hydrocarbon conversions involving dehydrogenation.

Contrast-enhanced CT with a High-Affinity Cationic Contrast Agent for Imaging ex Vivo Bovine, Intact ex Vivo Rabbit, and in Vivo Rabbit Cartilage

PubMed Central

Stewart, Rachel C.; Bansal, Prashant N.; Entezari, Vahid; Lusic, Hrvoje; Nazarian, Rosalynn M.; Snyder, Brian D.

2013-01-01

Purpose: To quantify the affinity of a cationic computed tomography (CT) contrast agent (CA4+) and that of an anionic contrast agent (ioxaglate) to glycosaminoglycans (GAGs) in ex vivo cartilage tissue explants and to characterize the in vivo diffusion kinetics of CA4+ and ioxaglate in a rabbit model. Materials and Methods: All in vivo procedures were approved by the institutional animal care and use committee. The affinities of ioxaglate and CA4+ to GAGs in cartilage (six bovine osteochondral plugs) were quantified by means of a modified binding assay using micro-CT after plug equilibration in serial dilutions of each agent. The contrast agents were administered intraarticularly to the knee joints of five New Zealand white rabbits to determine the in vivo diffusion kinetics and cartilage tissue imaging capabilities. Kinetics of diffusion into the femoral groove cartilage and relative contrast agent uptake into bovine plugs were characterized by means of nonlinear mixed-effects models. Diffusion time constants (τ) were compared by using a Student t test. Results: The uptake of CA4+ in cartilage was consistently over 100% of the reservoir concentration, whereas it was only 59% for ioxaglate. In vivo, the contrast material–enhanced cartilage reached a steady CT attenuation for both CA4+ and ioxaglate, with τ values of 13.8 and 6.5 minutes, respectively (P = .04). The cartilage was easily distinguishable from the surrounding tissues for CA4+ (12 mg of iodine per milliliter); comparatively, the anionic contrast agent provided less favorable imaging results, even when a higher concentration was used (80 mg of iodine per milliliter). Conclusion: The affinity of the cationic contrast agent CA4+ to GAGs enables high-quality imaging and segmentation of ex vivo bovine and rabbit cartilage, as well as in vivo rabbit cartilage. © RSNA, 2012 Supplemental material: http://radiology.rsna.org/lookup/suppl/doi:10.1148/radiol.12112246/-/DC1 PMID:23192774

Sorption of Sr, Co and Zn on illite: Batch experiments and modelling including Co in-diffusion measurements on compacted samples

NASA Astrophysics Data System (ADS)

Montoya, V.; Baeyens, B.; Glaus, M. A.; Kupcik, T.; Marques Fernandes, M.; Van Laer, L.; Bruggeman, C.; Maes, N.; Schäfer, T.

2018-02-01

Experimental investigations on the uptake of divalent cations (Sr, Co and Zn) onto illite (Illite du Puy, Le-Puy-en-Velay, France) were carried out by three different international research groups (Institute for Nuclear Waste Disposal, KIT (Germany), Group Waste & Disposal, SCK-CEN, (Belgium) and Laboratory for Waste Management, PSI (Switzerland)) in the framework of the European FP7 CatClay project. The dependence of solid-liquid distribution ratios (Rd values) on pH at trace metal conditions (sorption edges) and on the metal ion concentration (sorption isotherms) was determined in dilute suspensions of homo-ionic Na-illite (Na-IdP) under controlled N2 atmosphere. The experimental results were modelled using the 2 Site Protolysis Non Electrostatic Surface Complexation and Cation Exchange (2SPNE SC/CE) sorption model. The sorption of Sr depends strongly on ionic strength, while a rather weak pH dependence is observed in a pH range between 3 and 11. The data were modelled with cation exchange reactions, taking into account competition with H, K, Ca, Mg and Al, and surface complexation on weak amphotheric edge sites at higher pH values. The sorption of Co on Na-IdP, however, is strongly pH dependent. Cation exchange on the planar sites and surface complexation on strong and weak amphoteric edge sites were used to describe the Co sorption data. Rd values for Co derived from in-diffusion measurements on compacted Na-IdP samples (bulk-dry density of 1700 kg m-3) between pH 5.0 and 9.0 are in good agreement with the batch sorption data. The equivalence of both approaches to measure sorption was thus confirmed for the present test system. In addition, the results highlight the importance of both major and minor surface species for the diffusive transport behaviour of strongly sorbing metal cations. While surface complexes at the edge sites determine largely the Rd value, the diffusive flux may be governed by those species bound to the planar sites, even at low fractional occupancies. The pH dependent sorption determined for trace Zn concentrations showed large Rd values across the entire pH range with almost no dependence on the background electrolyte concentration. Additional sorption experiments carried out at substantial fractional Zn loadings demonstrated that the selectivity for the exchange of Na+ for Zn2+ at the planar sites could not explain the large Rd values measured at low pH and trace Zn concentrations. This suggests that another mechanism is ruling Zn uptake under these conditions.

Fluctuation-enhanced electric conductivity in electrolyte solutions.

PubMed

Péraud, Jean-Philippe; Nonaka, Andrew J; Bell, John B; Donev, Aleksandar; Garcia, Alejandro L

2017-10-10

We analyze the effects of an externally applied electric field on thermal fluctuations for a binary electrolyte fluid. We show that the fluctuating Poisson-Nernst-Planck (PNP) equations for charged multispecies diffusion coupled with the fluctuating fluid momentum equation result in enhanced charge transport via a mechanism distinct from the well-known enhancement of mass transport that accompanies giant fluctuations. Although the mass and charge transport occurs by advection by thermal velocity fluctuations, it can macroscopically be represented as electrodiffusion with renormalized electric conductivity and a nonzero cation-anion diffusion coefficient. Specifically, we predict a nonzero cation-anion Maxwell-Stefan coefficient proportional to the square root of the salt concentration, a prediction that agrees quantitatively with experimental measurements. The renormalized or effective macroscopic equations are different from the starting PNP equations, which contain no cross-diffusion terms, even for rather dilute binary electrolytes. At the same time, for infinitely dilute solutions the renormalized electric conductivity and renormalized diffusion coefficients are consistent and the classical PNP equations with renormalized coefficients are recovered, demonstrating the self-consistency of the fluctuating hydrodynamics equations. Our calculations show that the fluctuating hydrodynamics approach recovers the electrophoretic and relaxation corrections obtained by Debye-Huckel-Onsager theory, while elucidating the physical origins of these corrections and generalizing straightforwardly to more complex multispecies electrolytes. Finally, we show that strong applied electric fields result in anisotropically enhanced "giant" velocity fluctuations and reduced fluctuations of salt concentration.

The reduction mechanism of chromite in the presence of a silica flux

NASA Astrophysics Data System (ADS)

Weber, P.; Eric, R. H.

1993-12-01

The reduction behavior of a natural chromite from the Bushveld Complex of South Africa was studied at 1300 °C to 1500 °C. Reduction was by graphite in the presence of silica. Thermo-gravimetric analysis, X-ray diffraction (XRD) analysis, energy-dispersive X-ray analysis (EDAX), and metallographic analysis were the experimental techniques used. Silica affected the reduction at and above 1400 °C. A two-stage reduction mechanism was established. The first stage, up to a reduction level of about 40 pct, is primarily confined to iron metallization, and zoning is observed in partially reduced chromites. In this stage, silica does not interfere with the reduction, which proceeds by an outward diffusion of Fe2+ ions and an inward diffusion of Mg2+ and Cr2+ ions. The second stage is primarily confined to chromium metallization, and formation of a silicate slag alters the reduction mechanism. The slag phase agglomerates and even embeds partially reduced chromite particles. An ion-exchange reaction between the re-ducible cations (Cr3+ and Fe2+) in the spinel and the dissolved cations (Al3+ and Mg2+) in the slag allows further reduction. Once the reducible cations are dissolved in the slag phase, they are reduced to the metallic state at sites where there is contact with the reductant.

Impact of ionic liquids in aqueous solution on bacterial plasma membranes studied with molecular dynamics simulations.

PubMed

Lim, Geraldine S; Zidar, Jernej; Cheong, Daniel W; Jaenicke, Stephan; Klähn, Marco

2014-09-04

The impact of five different imidazolium-based ionic liquids (ILs) diluted in water on the properties of a bacterial plasma membrane is investigated using molecular dynamics (MD) simulations. Cations considered are 1-octyl-3-methylimidazolium (OMIM), 1-octyloxymethyl-3-methylimidazolium (OXMIM), and 1-tetradecyl-3-methylimidazolium (TDMIM), as well as the anions chloride and lactate. The atomistic model of the membrane bilayer is designed to reproduce the lipid composition of the plasma membrane of Gram-negative Escherichia coli. Spontaneous insertion of cations into the membrane is observed in all ILs. Substantially more insertions of OMIM than of OXMIM occur and the presence of chloride reduces cation insertions compared to lactate. In contrast, anions do not adsorb onto the membrane surface nor diffuse into the bilayer. Once inserted, cations are oriented in parallel to membrane lipids with cation alkyl tails embedded into the hydrophobic membrane core, while the imidazolium-ring remains mostly exposed to the solvent. Such inserted cations are strongly associated with one to two phospholipids in the membrane. The overall order of lipids decreased after OMIM and OXMIM insertions, while on the contrary the order of lipids in the vicinity of TDMIM increased. The short alkyl tails of OMIM and OXMIM generate voids in the bilayer that are filled by curling lipids. This cation induced lipid disorder also reduces the average membrane thickness. This effect is not observed after TDMIM insertions due to the similar length of cation alkyl chain and the fatty acids of the lipids. This lipid-mimicking behavior of inserted TDMIM indicates a high membrane affinity of this cation that could lead to an enhanced accumulation of cations in the membrane over time. Overall, the simulations reveal how cations are inserted into the bacterial membrane and how such insertions change its properties. Moreover, the different roles of cations and anions are highlighted and the fundamental importance of cation alkyl chain length and its functionalization is demonstrated.

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

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

Marceau, François, E-mail: francois.marceau@crchul.ulaval.ca; Bawolak, Marie-Thérèse; Lodge, Robert

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

Role of cations as components of jelly coats in Bufo arenarum fertilization.

PubMed

Medina, Marcela Fátima; Crespo, Claudia Alejandra; Ramos, Inés; Fernández, Silvia Nélida

2010-02-01

The role of monovalent (Na+, K+) and divalent (Ca2+, Mg2+) cations in Bufo arenarum fertilization was analysed. Our results showed that the highest fertilization percentages were obtained when strings of uterine oocytes (UO) were inseminated. Under these conditions, full jelly (FJ), which represents the jelly coats surrounding the oocytes at the time of deposition, contained 68.5 +/- 7.0 mM Na+, 27.4 +/- 2.4 mM K+, 6.3 +/- 0.9 mM Ca2+ and 6.9 +/- 0.9 mM Mg2+. When the strings of oocytes were washed in deionized water, these cations diffused into the liquid medium surrounding them. There was a marked similarity between the loss of Ca2+ in the jelly and the decrease in the fertilizability of the UO. Furthermore, the use of chelating agents of divalent cations showed the importance of the Ca2+ contained in the jelly. When Ca2+ was sequestered from the jelly coats by the addition of the chelating agents to the insemination medium as well as by pretreatment of the UO strings, a decrease in fertilization percentages occurred, this effect being dose dependent and more marked with EGTA. These results demonstrate that the Ca2+ in the jelly plays a role in fertilization. Nevertheless, taking into account that during the washing of the jelly other jelly coat components were diffused and considering that the addition of Ca2+ to the insemination medium reverted significantly, but only partially, the loss of fertilizability of jellied UO (washed), the participation of other components in the fertilization mechanism is suggested.

Determination of the zincate diffusion coefficient and its application to alkaline battery problems

NASA Technical Reports Server (NTRS)

May, C. E.; Kautz, Harold E.

1978-01-01

The diffusion coefficient for the zincate ion at 24 C was found to be 9.9 X 10 to the minus 7th power squared cm per sec + or - 30 percent in 45 percent potassium hydroxide and 1.4 x 10 to the minus 7 squared cm per sec + or - 25 percent in 40 percent sodium hydroxide. Comparison of these values with literature values at different potassium hydroxide concentrations show that the Stokes-Einstein equation is obeyed. The diffusion coefficient is characteristic of the zincate ion (not the cation) and independent of its concentration. Calculations with the measured value of the diffusion coefficient show that the zinc concentration in an alkaline zincate half cell becomes uniform throughout in tens of hours by diffusion alone. Diffusion equations are derived which are applicable to finite size chambers. Details and discussion of the experimental method are also given.

Determination of the zincate diffusion coefficient and its application to alkaline battery problems

NASA Technical Reports Server (NTRS)

May, C. E.; Kautz, H. E.

1978-01-01

The diffusion coefficient for the zincate ion at 24 C was found to be 9.9 x 10 to the -7th power sq cm/sec + or - 30% in 45% potassium hydroxide and 1.4 x 10 to the -7th power sq cm/sec + or - 25% in 40% sodium hydroxide. Comparison of these values with literature values at different potassium hydroxide concentrations show that the Stokes-Einstein equation is obeyed. The diffusion coefficient is characteristic of the zincate ion (not the cation) and independent of its concentration. Calculations with the measured value of the diffusion coefficient show that the zinc concentration in an alkaline zincate half-cell becomes uniform throughout in tens of hours by diffusion alone. Diffusion equations are derived which are applicable to finite-size chambers. Details and discussion of the experimental method are also given.

Electronic Absorption Spectra of Mass-Selected Hydrocarbon Cations in Solid Neon: C_nH_4+ (n=5-8,10,12)

NASA Astrophysics Data System (ADS)

Nagy, A.; Fulara, J.; Garkusha, I.; Maier, J. P.

2011-05-01

Small, unsaturated hydrocarbons, C_nH_m (n,m≤6), play an important role in astrochemical models as they have been detected in various space objects such as the interstellar medium or envelopes of carbon-rich stars. Although identification of most of these species was based on rotational studies, they are candidate carriers of the infamous diffuse interstellar bands. It has been proposed that corresponding cationic species formed upon UV radiation may also be of astrophysical relevance; therefore, their optical spectra need to be determined. In this contribution, electronic absorption spectra of mass-selected C_nH_4+ (n=5-8,10,12) ions trapped in neon matrices are presented. The cations were produced in a hot-cathode discharge source, guided through a series of electrostatic lenses, mass filtered and co-deposited with excess of neon onto a rhodium-coated sapphire plate held at 6 K. In the same experiments, neutral species were generated from the cations by a photobleaching procedure.

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

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

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

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

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

DOE PAGES

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

2017-10-04

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

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

Emin, David, E-mail: emin@unm.edu; Akhtari, Massoud; Ellingson, B. M.

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

Structure and dynamics of solvated polyethylenimine chains

NASA Astrophysics Data System (ADS)

Beu, Titus A.; Farcaş, Alexandra

2017-12-01

Polimeric gene-delivery carriers have attracted great interest in recent years, owing to their applicability in gene therapy. In particular, cationic polymers represent the most promising delivery vectors for nucleic acids into the cells. This study presents extensive atomistic molecular dynamics simulations of linear polyethylenimine chains. The simulations show that the variation of the chain size and protonation fraction causes a substantial change of the diffusion coefficient. Examination of the solvated chains suggests the possibility of controlling the polymer diffusion mobility in solution.

Structure, Kinetics, and Thermodynamics of the Aqueous Uranyl(VI) Cation

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

Kerisit, Sebastien N.; Liu, Chongxuan

2013-08-20

Molecular simulation techniques are employed to gain insights into the structural, kinetic, and thermodynamic properties of the uranyl(VI) cation (UO22+) in aqueous solution. The simulations make use of an atomistic potential model (force field) derived in this work and based on the model of Guilbaud and Wipff (Guilbaud, P.; Wipff, G. J. Mol. Struct. (THEOCHEM) 1996, 366, 55-63). Reactive flux and thermodynamic integration calculations show that the derived potential model yields predictions for the water exchange rate and free energy of hydration, respectively, that are in agreement with experimental data. The water binding energies, hydration shell structure, and self-diffusion coefficientmore » are also calculated and discussed. Finally, a combination of metadynamics and transition path sampling simulations is employed to probe the mechanisms of water exchange reactions in the first hydration shell of the uranyl ion. These atomistic simulations indicate, based on two-dimensional free energy surfaces, that water exchanges follow an associative interchange mechanism. The nature and structure of the water exchange transition states are also determined. The improved potential model is expected to lead to more accurate predictions of uranyl adsorption energies at mineral surfaces using potential-based molecular dynamics simulations.« less

Interplay of electrostatics and lipid packing determines the binding of charged polymer coated nanoparticles to model membranes.

PubMed

Biswas, Nupur; Bhattacharya, Rupak; Saha, Arindam; Jana, Nikhil R; Basu, Jaydeep K

2015-10-07

Understanding of nanoparticle-membrane interactions is useful for various applications of nanoparticles like drug delivery and imaging. Here we report on the studies of interaction between hydrophilic charged polymer coated semiconductor quantum dot nanoparticles with model lipid membranes. Atomic force microscopy and X-ray reflectivity measurements suggest that cationic nanoparticles bind and penetrate bilayers of zwitterionic lipids. Penetration and binding depend on the extent of lipid packing and result in the disruption of the lipid bilayer accompanied by enhanced lipid diffusion. On the other hand, anionic nanoparticles show minimal membrane binding although, curiously, their interaction leads to reduction in lipid diffusivity. It is suggested that the enhanced binding of cationic QDs at higher lipid packing can be understood in terms of the effective surface potential of the bilayers which is tunable through membrane lipid packing. Our results bring forth the subtle interplay of membrane lipid packing and electrostatics which determine nanoparticle binding and penetration of model membranes with further implications for real cell membranes.

Differential Microscopic Mobility of Components within a Deep Eutectic Solvent

DOE PAGES

Wagle, Durgesh V.; Baker, Gary A.; Mamontov, Eugene

2015-07-13

From macroscopic measurements of deep eutectic solvents such as glyceline (1:2 molar ratio of choline chloride to glycerol), the long-range translational diffusion of the larger cation (choline) is known to be slower compared to that of the smaller hydrogen bond donor (glycerol). However, when the diffusion dynamics are analyzed on the subnanometer length scale, we discover that the displacements associated with the localized diffusive motions are actually larger for choline. This counterintuitive diffusive behavior can be understood as follows. The localized diffusive motions confined in the transient cage of neighbor particles, which precede the cage-breaking long-range diffusion jumps, are moremore » spatially constrained for glycerol than for choline because of the stronger hydrogen bonds the former makes with chloride anions. The implications of differential localized mobility of the constituents should be especially important for applications where deep eutectic solvents are confined on the nanometer length scale and their long-range translational diffusion is strongly inhibited (e.g., within microporous media).« less

Detection of Buckminsterfullerene emission in the diffuse interstellar medium.

PubMed

Berné, O; Cox, N L J; Mulas, G; Joblin, C

2017-09-01

Emission of fullerenes in their infrared vibrational bands has been detected in space near hot stars. The proposed attribution of the diffuse interstellar bands at 9577 and 9632 Å to electronic transitions of the buckminsterfullerene cation (i.e. [Formula: see text]) was recently supported by new laboratory data, confirming the presence of this species in the diffuse interstellar medium (ISM). In this letter, we present the detection, also in the diffuse ISM, of the 17.4 and 18.9 μ m emission bands commonly attributed to vibrational bands of neutral C 60 . According to classical models that compute the charge state of large molecules in space, C 60 is expected to be mostly neutral in the diffuse ISM. This is in agreement with the abundances of diffuse C 60 we derive here from observations. We also find that C 60 is less abundant in the diffuse ISM than in star-forming regions, supporting the theory that C 60 can be formed in these regions.

Mesoporous nanocrystalline film architecture for capacitive storage devices

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

Dunn, Bruce S.; Tolbert, Sarah H.; Wang, John

A mesoporous, nanocrystalline, metal oxide construct particularly suited for capacitive energy storage that has an architecture with short diffusion path lengths and large surface areas and a method for production are provided. Energy density is substantially increased without compromising the capacitive charge storage kinetics and electrode demonstrates long term cycling stability. Charge storage devices with electrodes using the construct can use three different charge storage mechanisms immersed in an electrolyte: (1) cations can be stored in a thin double layer at the electrode/electrolyte interface (non-faradaic mechanism); (2) cations can interact with the bulk of an electroactive material which then undergoesmore » a redox reaction or phase change, as in conventional batteries (faradaic mechanism); or (3) cations can electrochemically adsorb onto the surface of a material through charge transfer processes (faradaic mechanism).« less

Examination of the nature of lattice matched III V semiconductor interfaces using computer simulated molecular beam epitaxial growth I. AC/BC interfaces

NASA Astrophysics Data System (ADS)

Thomsen, M.; Ghaisas, S. V.; Madhukar, A.

1987-07-01

A previously developed computer simulation of molecular beam epitaxial growth of III-V semiconductors based on the configuration dependent reactive incorporation (CDRI) model is extended to allow for two different cation species. Attention is focussed on examining the nature of interfaces formed in lattice matched quantum well structures of the form AC/BC/AC(100). We consider cation species with substantially different effective diffusion lengths, as is the case with Al and Ga during the growth of their respective As compounds. The degree of intermixing occuring at the interface is seen to be dependent upon, among other growth parameters, the pressure of the group V species during growth. Examination of an intraplanar order parameter at the interfaces reveals the existence of short range clustering of the cation species.

Development of a numerical model for the electric current in burner-stabilised methane-air flames

NASA Astrophysics Data System (ADS)

Speelman, N.; de Goey, L. P. H.; van Oijen, J. A.

2015-03-01

This study presents a new model to simulate the electric behaviour of one-dimensional ionised flames and to predict the electric currents in these flames. The model utilises Poisson's equation to compute the electric potential. A multi-component diffusion model, including the influence of an electric field, is used to model the diffusion of neutral and charged species. The model is incorporated into the existing CHEM1D flame simulation software. A comparison between the computed electric currents and experimental values from the literature shows good qualitative agreement for the voltage-current characteristic. Physical phenomena, such as saturation and the diodic effect, are captured by the model. The dependence of the saturation current on the equivalence ratio is also captured well for equivalence ratios between 0.6 and 1.2. Simulations show a clear relation between the saturation current and the total number of charged particles created. The model shows that the potential at which the electric field saturates is strongly dependent on the recombination rate and the diffusivity of the charged particles. The onset of saturation occurs because most created charged particles are withdrawn from the flame and because the electric field effects start dominating over mass based diffusion. It is shown that this knowledge can be used to optimise ionisation chemistry mechanisms. It is shown numerically that the so-called diodic effect is caused primarily by the distance the heavier cations have to travel to the cathode.

Kinetics of intercalation of fluorescent probes in magnesium–aluminium layered double hydroxide within a multiscale reaction–diffusion framework

PubMed Central

Saliba, Daniel

2016-01-01

We report the synthesis of magnesium–aluminium layered double hydroxide (LDH) using a reaction–diffusion framework (RDF) that exploits the multiscale coupling of molecular diffusion with chemical reactions, nucleation and growth of crystals. In an RDF, the hydroxide anions are allowed to diffuse into an organic gel matrix containing the salt mixture needed for the precipitation of the LDH. The chemical structure and composition of the synthesized magnesium–aluminium LDHs are determined using powder X-ray diffraction (PXRD), thermo-gravimetric analysis, differential scanning calorimetry, solid-state nuclear magnetic resonance (SSNMR), Fourier transform infrared and energy dispersive X-ray spectroscopy. This novel technique also allows the investigation of the mechanism of intercalation of some fluorescent probes, such as the neutral three-dimensional rhodamine B (RhB) and the negatively charged two-dimensional 8-hydroxypyrene-1,3,6-trisulfonic acid (HPTS), using in situ steady-state fluorescence spectroscopy. The incorporation of these organic dyes inside the interlayer region of the LDH is confirmed via fluorescence microscopy, solid-state lifetime, SSNMR and PXRD. The activation energies of intercalation of the corresponding molecules (RhB and HPTS) are computed and exhibit dependence on the geometry of the involved probe (two or three dimensions), the charge of the fluorescent molecule (anionic, cationic or neutral) and the cationic ratio of the corresponding LDH. This article is part of the themed issue ‘Multiscale modelling at the physics–chemistry–biology interface’. PMID:27698034

Transport of water and ions in partially water-saturated porous media. Part 2. Filtration effects

NASA Astrophysics Data System (ADS)

Revil, A.

2017-05-01

A new set of constitutive equations describing the transport of the ions and water through charged porous media and considering the effect of ion filtration is applied to the problem of reverse osmosis and diffusion of a salt. Starting with the constitutive equations derived in Paper 1, I first determine specific formula for the osmotic coefficient and effective diffusion coefficient of a binary symmetric 1:1 salt (such as KCl or NaCl) as a function of a dimensionless number Θ corresponding to the ratio between the cation exchange capacity (CEC) and the salinity. The modeling is first carried with the Donnan model used to describe the concentrations of the charge carriers in the pore water phase. Then a new model is developed in the thin double layer approximation to determine these concentrations. These models provide explicit relationships between the concentration of the ionic species in the pore space and those in a neutral reservoir in local equilibrium with the pore space and the CEC. The case of reverse osmosis and diffusion coefficient are analyzed in details for the case of saturated and partially saturated porous materials. Comparisons are done with experimental data from the literature obtained on bentonite. The model predicts correctly the influence of salinity (including membrane behavior at high salinities), porosity, cation type (K+ versus Na+), and water saturation on the osmotic coefficient. It also correctly predicts the dependence of the diffusion coefficient of the salt with the salinity.

Kinetics of intercalation of fluorescent probes in magnesium-aluminium layered double hydroxide within a multiscale reaction-diffusion framework

NASA Astrophysics Data System (ADS)

Saliba, Daniel; Al-Ghoul, Mazen

2016-11-01

We report the synthesis of magnesium-aluminium layered double hydroxide (LDH) using a reaction-diffusion framework (RDF) that exploits the multiscale coupling of molecular diffusion with chemical reactions, nucleation and growth of crystals. In an RDF, the hydroxide anions are allowed to diffuse into an organic gel matrix containing the salt mixture needed for the precipitation of the LDH. The chemical structure and composition of the synthesized magnesium-aluminium LDHs are determined using powder X-ray diffraction (PXRD), thermo-gravimetric analysis, differential scanning calorimetry, solid-state nuclear magnetic resonance (SSNMR), Fourier transform infrared and energy dispersive X-ray spectroscopy. This novel technique also allows the investigation of the mechanism of intercalation of some fluorescent probes, such as the neutral three-dimensional rhodamine B (RhB) and the negatively charged two-dimensional 8-hydroxypyrene-1,3,6-trisulfonic acid (HPTS), using in situ steady-state fluorescence spectroscopy. The incorporation of these organic dyes inside the interlayer region of the LDH is confirmed via fluorescence microscopy, solid-state lifetime, SSNMR and PXRD. The activation energies of intercalation of the corresponding molecules (RhB and HPTS) are computed and exhibit dependence on the geometry of the involved probe (two or three dimensions), the charge of the fluorescent molecule (anionic, cationic or neutral) and the cationic ratio of the corresponding LDH. This article is part of the themed issue 'Multiscale modelling at the physics-chemistry-biology interface'.

Transient cerebral hypoperfusion assisted intraarterial cationic liposome delivery to brain tissue

PubMed Central

Joshi, Shailendra; Singh-Moon, Rajinder P.; Wang, Mei; Chaudhuri, Durba B.; Holcomb, Mark; Straubinger, Ninfa L.; Bruce, Jeffrey N.; Bigio, Irving J.; Straubinger, Robert M.

2014-01-01

Object Transient cerebral hypoperfusion (TCH) has empirically been used to assist intraarterial (IA) drug delivery to brain tumors. Transient (< 3 min) reduction of cerebral blood flow (CBF) occurs during many neuro- and cardiovascular interventions and has recently been used to better target IA drugs to brain tumors. In the present experiments, we assessed whether the effectiveness of IA delivery of cationic liposomes could be improved by TCH. Methods Cationic liposomes composed of 1:1 DOTAP:PC (dioleoyl-trimethylammonium-propane:phosphatidylcholine) were administered to three groups of Sprague Dawley rats. In the first group, we tested the effect of blood flow reduction on IA delivery of cationic liposomes. In the second group, we compared TCH-assisted IA liposomal delivery vs. intravenous (IV) administration of the same dose. In the third group, we assessed retention of cationic liposomes in brain four hours after TCH assisted delivery. The liposomes contained a near infrared dye, DilC18(7), whose concentration could be measured in vivo by diffuse reflectance spectroscopy. Results IA injections of cationic liposomes during TCH increased their delivery approximately four-fold compared to injections during normal blood flow. Optical pharmacokinetic measurements revealed that relative to IV injections, IA injection of cationic liposomes during TCH produced tissue concentrations that were 100-fold greater. The cationic liposomes were retained in the brain tissue four hours after a single IA injection. There was no gross impairment of neurological functions in surviving animals. Conclusions Transient reduction in CBF significantly increased IA delivery of cationic liposomes in the brain. High concentrations of liposomes could be delivered to brain tissue after IA injections with concurrent TCH while none could be detected after IV injection. IA-TCH injections were well tolerated and cationic liposomes were retained for at least 4 hours after IA administration. These results should encourage development of cationic liposomal formulations of chemotherapeutic drugs and their IA delivery during TCH. PMID:24664370

Transport, electrochemical and thermophysical properties of two N-donor-functionalised ionic liquids.

PubMed

Rüther, Thomas; Harris, Kenneth R; Horne, Michael D; Kanakubo, Mitsuhiro; Rodopoulos, Theo; Veder, Jean-Pierre; Woolf, Lawrence A

2013-12-23

Two N-donor-functionalised ionic liquids (ILs), 1-ethyl-1,4-dimethylpiperazinium bis(trifluoromethylsulfonyl)amide (1) and 1-(2-dimethylaminoethyl)-dimethylethylammonium bis(trifluoromethylsulfonyl)amide (2), were synthesised and their electrochemical and transport properties measured. The data were compared with the benchmark system, N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (3). Marked differences in thermal and electrochemical stability were observed between the two tertiary-amine-functionalised salts and the non-functionalised benchmark. The former are up to 170 K and 2 V less stable than the structural counterpart lacking a tertiary amine function. The ion self-diffusion coefficients (Di ) and molar conductivities (Λ) are higher for the IL with an open-chain cation (2) than that with a cyclic cation (1), but less than that with a non-functionalised, heterocyclic cation (3). The viscosities (η) show the opposite behaviour. The Walden [Λ[proportionality](1/η)(t) ] and Stokes-Einstein [Di /T)[proportionality](1/η)(t) ] exponents, t, are very similar for the three salts, 0.93-0.98 (±0.05); that is, the self-diffusion coefficients and conductivity are set by η. The Di for 1 and 2 are the same, within experimental error, at the same viscosity, whereas Λ for 1 is approximately 13% higher than that of 2. The diffusion and molar conductivity data are consistent, with a slope of 0.98±0.05 for a plot of ln(ΛT) against ln(D+ +D- ). The Nernst-Einstein deviation parameters (Δ) are such that the mean of the two like-ion VCCs is greater than that of the unlike ions. The values of Δ are 0.31, 0.36 and 0.42 for 3, 1 and 2, respectively, as is typical for ILs, but there is some subtlety in the ion interactions given 2 has the largest value. The distinct diffusion coefficients (DDC) follow the order D(d)__ < D(d)++ < D(d)+_, as is common for [Tf2N](-) salts. The ion motions are not correlated as in an electrolyte solution: instead, there is greater anti-correlation between the velocities of a given anion and the overall ensemble of anions in comparison to those for the cationic analogue, the anti-correlation for the velocities of which is in turn greater than that for a given ion and the ensemble of oppositely charged ions, an observation that is due to the requirement for the conservation of momentum in the system. The DDC also show fractional SE behaviour with t~0.95. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Forest soil mineral weathering rates: use of multiple approaches

Treesearch

Randy K. Kolka; D.F. Grigal; E.A. Nater

1996-01-01

Knowledge of rates of release of base cations from mineral dissolution (weathering) is essential to understand ecosystem elemental cycling. Although much studied, rates remain enigmatic. We compared the results of four methods to determine cation (Ca + Mg + K) release rates at five forested soils/sites in the northcentral U.S.A. Our premise was that multiple...

Investigation of Dynamics in BMIM TFSA Ionic Liquid through Variable Temperature and Pressure NMR Relaxometry and Diffusometry

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

Pilar, Kartik; Rua, Armando; Suarez, Sophia N.

A comprehensive variable temperature, pressure and frequency multinuclear ( 1H, 2H, and 19F) magnetic resonance study was undertaken on selectively deuterated 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (BMIM TFSA) ionic liquid isotopologues. This study builds on our earlier investigation of the effects of increasing alkyl chain length on diffusion and dynamics in imidazolium-based TFSA ionic liquids. Fast field cycling 1H T 1 data revealed multiple modes of motion. Through calculation of diffusion coefficient (D) values and activation energies, the low- and high-field regimes were assigned to the translational and reorientation dynamics respectively. Variable-pressure 2H T 1 measurements reveal site-dependent interactions in the cation withmore » strengths in the order MD 3 > CD 3 > CD 2, indicating dissimilarities in the electric field gradients along the alkyl chain, with the CD 2 sites having the largest gradient. Additionally, the α saturation effect in T 1 vs. P was observed for all three sites, suggesting significant reduction of the short-range rapid reorientational dynamics. This reduction was also deduced from the variable pressure 1H T 1 data, which showed an approach to saturation for both the methyl and butyl group terminal methyl sites. Pressure-dependent D measurements show independent motions for both cations and anions, with the cations having greater D values over the entire pressure range.« less

The bundling of actin with polyethylene glycol 8000 in the presence and absence of gelsolin.

PubMed Central

Goverman, J; Schick, L A; Newman, J

1996-01-01

Actin filament and bundle formation occur in the cytosol under conditions of very high total macromolecular concentration. In this study we have utilized the inert molecule polyethylene glycol 8000 (PEG) as a means of simulating crowded conditions in vitro. Column-purified Ca-actin was polymerized in the absence and presence of gelsolin (to regulate mean filament lengths between 50 and 5000 mers) and PEG (2-8%) using various concentrations of KCl and/or 2 mM divalent cations. Bundling was characterized by the scattered light intensity and mean diffusion coefficients obtained from dynamic light scattering, as well as by fluorescence and phase-contrast microscopy. The minimum concentration of KCl required for bundling decreases both with increasing concentration of PEG at a fixed mean filament length, and with decreasing filament length at a fixed concentration of PEG. In the absence of divalent cation, bundling is reversible on dilution, as determined by intensity levels, diffusion coefficients, and microscopy. However, with either 2 mM Mg2+ or Ca2+ added, bundling is irreversible under conditions of higher PEG concentrations or longer filaments, indicating that osmotic pressure effects cannot fully explain actin bundling with PEG. Weaker divalent cation-binding sites on actin as well as disulfide bonds appear to be involved in the irreversible bundling. Images FIGURE 7 PMID:8874022

Investigation of Dynamics in BMIM TFSA Ionic Liquid through Variable Temperature and Pressure NMR Relaxometry and Diffusometry

DOE PAGES

Pilar, Kartik; Rua, Armando; Suarez, Sophia N.; ...

2017-05-11

A comprehensive variable temperature, pressure and frequency multinuclear ( 1H, 2H, and 19F) magnetic resonance study was undertaken on selectively deuterated 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (BMIM TFSA) ionic liquid isotopologues. This study builds on our earlier investigation of the effects of increasing alkyl chain length on diffusion and dynamics in imidazolium-based TFSA ionic liquids. Fast field cycling 1H T 1 data revealed multiple modes of motion. Through calculation of diffusion coefficient (D) values and activation energies, the low- and high-field regimes were assigned to the translational and reorientation dynamics respectively. Variable-pressure 2H T 1 measurements reveal site-dependent interactions in the cation withmore » strengths in the order MD 3 > CD 3 > CD 2, indicating dissimilarities in the electric field gradients along the alkyl chain, with the CD 2 sites having the largest gradient. Additionally, the α saturation effect in T 1 vs. P was observed for all three sites, suggesting significant reduction of the short-range rapid reorientational dynamics. This reduction was also deduced from the variable pressure 1H T 1 data, which showed an approach to saturation for both the methyl and butyl group terminal methyl sites. Pressure-dependent D measurements show independent motions for both cations and anions, with the cations having greater D values over the entire pressure range.« less

CATAPHORETIC CHARGES OF COLLODION PARTICLES AND ANOMALOUS OSMOSIS THROUGH COLLODION MEMBRANES FREE FROM PROTEIN

PubMed Central

Loeb, Jacques

1922-01-01

1. It had been shown in previous papers that when a salt solution is separated from pure water by a collodion membrane, water diffuses through the membrane as if it were positively charged and as if it were attracted by the anion of the salt in solution and repelled by the cation with a force increasing with the valency. In this paper, measurements of the P.D. across the membrane (E) are given, showing that when an electrical effect is added to the purely osmotic effect of the salt solution in the transport of water from the side of pure water to the solution, the latter possesses a considerable negative charge which increases with increasing valency of the anion of the salt and diminishes with increasing valency of the cation. It is also shown that a similar valency effect exists in the diffusion potentials between salt solutions and pure water without the interposition of a membrane. 2. This makes it probable that the driving force for the electrical transport of water from the side of pure water into solution is primarily a diffusion potential. 3. It is shown that the hydrogen ion concentration of the solution affects the transport curves and the diffusion potentials in a similar way. 4. It is shown, however, that the diffusion potential without interposition of the membrane differs in a definite sense from the P.D. across the membrane and that therefore the P.D. across the membrane (E) is a modified diffusion potential. 5. Measurements of the P.D. between collodion particles and aqueous solutions (ε) were made by the method of cataphoresis, which prove that water in contact with collodion particles free from protein practically always assumes a positive charge (except in the presence of salts with trivalent and probably tetravalent cations of a sufficiently high concentration). 6. It is shown that an electrical transport of water from the side of water into the solution is always superposed upon the osmotic transport when the sign of charge of the solution in the potential across the membrane (E) is opposite to that of the water in the P.D. between collodion particle and water (ε); supporting the theoretical deductions made by Bartell. 7. It is shown that the product of the P.D. across the membrane (E) into the cataphoretic P.D. between collodion particles and aqueous solution (ε) accounts in general semiquantitatively for that part of the transport of water into the solution which is due to the electrical forces responsible for anomalous osmosis. PMID:19871981

Determination of diffusion coefficients of various livestock antibiotics in water at infinite dilution

NASA Astrophysics Data System (ADS)

Soriano, Allan N.; Adamos, Kristoni G.; Bonifacio, Pauline B.; Adornado, Adonis P.; Bungay, Vergel C.; Vairavan, Rajendaran

2017-11-01

The fate of antibiotics entering the environment raised concerns on the possible effect of antimicrobial resistance bacteria. Prediction of the fate and transport of these particles are needed to be determined, significantly the diffusion coefficient of antibiotic in water at infinite dilution. A systematic determination of diffusion coefficient of antibiotic in water at infinite dilution of five different kinds of livestock antibiotics namely: Amtyl, Ciprotyl, Doxylak Forte, Trisullak, and Vetracin Gold in the 293.15 to 313.15 K temperature range are reported through the use of the method involving the electrolytic conductivity measurements. A continuous stirred tank reactor is utilized to measure the electrolytic conductivities of the considered systems. These conductivities are correlated by using the Nernst-Haskell equation to determine the infinite dilution diffusion coefficient. Determined diffusion coefficients are based on the assumption that in dilute solution, these antibiotics behave as strong electrolyte from which H+ cation dissociate from the antibiotic's anion.

Garnet zoning and metamorphism of the Barrovian type area, Scotland

NASA Astrophysics Data System (ADS)

Dempster, T. J.

1985-03-01

A microprobe investigation of the high grade metamorphic zones from the Barrovian type area in Angus, Scotland, shows the importance of local zones of retrograde cation exchange between garnet, staurolite and biotite. The interpretation of this zoning, established during a slow cooling history, is critical to any study of metamorphic reactions or conditions. The extent and intensity of these diffusion effects are dependent on a number of parameters including grainsize, fabric orientation, heating and cooling history, and the modal abundance of the phases. Increasing diffusion within garnets with metamorphic grade, and the subsequent retrograde effects are modelled using Temperature-Time-Transformation diagrams and provide information on the activation energy for Fe-Mg diffusion in garnet.

Electrolyte Engineering: Optimizing High-Rate Double-Layer Capacitances of Micropore- and Mesopore-Rich Activated Carbon.

PubMed

Chen, Ting-Hao; Yang, Cheng-Hsien; Su, Ching-Yuan; Lee, Tai-Chou; Dong, Quan-Feng; Chang, Jeng-Kuei

2017-09-22

Various types of electrolyte cations as well as binary cations are used to optimize the capacitive performance of activated carbon (AC) with different pore structures. The high-rate capability of micropore-rich AC, governed by the mobility of desolvated cations, can outperform that of mesopore-rich AC, which essentially depends on the electrolyte conductivity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorption properties of cationic rhodamine B dye onto metals chloride-activated castor bean residue carbons.

PubMed

Zhi, Lee Lin; Zaini, Muhammad Abbas Ahmad

2017-02-01

This work was aimed to evaluate the feasibility of castor bean residue based activated carbons prepared through metals chloride activation. The activated carbons were characterized for textural properties and surface chemistry, and the adsorption data of rhodamine B were established to investigate the removal performance. Zinc chloride-activated carbon with specific surface area of 395 m 2 /g displayed a higher adsorption capacity of 175 mg/g. Magnesium chloride and iron(III) chloride are less toxic and promising agents for composite chemical activation. The adsorption data obeyed Langmuir isotherm and pseudo-second-order kinetics model. The rate-limiting step in the adsorption of rhodamine B is film diffusion. The positive values of enthalpy and entropy indicate that the adsorption is endothermic and spontaneous at high temperature.

Ion Dynamics in a Mixed-Cation Alkoxy-Ammonium Ionic Liquid Electrolyte for Sodium Device Applications.

PubMed

Pope, Cameron R; Kar, Mega; MacFarlane, Douglas R; Armand, Michel; Forsyth, Maria; O'Dell, Luke A

2016-10-18

The ion dynamics in a novel sodium-containing room-temperature ionic liquid (IL) consisting of an ether-functionalised quaternary ammonium cation and bis(trifluoromethylsulfonyl)amide [NTf 2 ] anion with various concentrations of Na[NTf 2 ] have been characterised using differential scanning calorimetry, impedance spectroscopy, diffusometry and NMR relaxation measurements. The IL studied has been specifically designed to dissolve a relatively large concentration of Na[NTf 2 ] salt (over 2 mol kg -1 ) as this has been shown to improve ion transport and conductivity. Consistent with other studies, the measured ionic conductivity and diffusion coefficients show that the overall ionic mobility decreases with decreasing temperature and increasing salt content. NMR relaxation measurements provide evidence for correlated dynamics between the ether-functionalised ammonium and Na cations, possibly with the latter species acting as cross-links between multiple ammonium cations. Finally, preliminary cyclic voltammetry experiments show that this IL can undergo stable electrochemical cycling and could therefore be potentially useful as an electrolyte in a Na-based device. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed Central

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

2015-01-01

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

Oxygen diffusion in Gd-doped mixed oxides

DOE PAGES

Galvin, C. O. T.; Cooper, M. W. D.; Rushton, M. J. D.; ...

2017-10-23

Molecular dynamics simulations have been performed to investigate oxygen transport in (U xPu x-1) 0.95Gd 0.05O 1.975, (U xTh x-1) 0.95Gd 0.05O 1.975 and (Pu xTh x-1) 0.95Gd 0.05O 1.975 between 1000 and 3200 K. Oxygen diffusivity and corresponding activation energies are examined and compared to values for the undoped (U xPu x-1)O 2, (U xTh x-1)O 2 and (Pu xTh x-1)O 2 systems where compositions between end members display enhanced diffusivity. Below the superionic transition oxygen diffusivity for the Gd doped systems is orders of magnitude greater compared to their undoped counterparts. But, enhanced diffusivity for doped mixed actinidemore » cation compositions is not observed compared to doped end members. Furthermore, changes in activation energy suggest changes in diffusion regime, which correspond to the creation of thermally activated oxygen defects.« less

Oxygen diffusion in Gd-doped mixed oxides

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

Galvin, C. O. T.; Cooper, M. W. D.; Rushton, M. J. D.

Molecular dynamics simulations have been performed to investigate oxygen transport in (U xPu x-1) 0.95Gd 0.05O 1.975, (U xTh x-1) 0.95Gd 0.05O 1.975 and (Pu xTh x-1) 0.95Gd 0.05O 1.975 between 1000 and 3200 K. Oxygen diffusivity and corresponding activation energies are examined and compared to values for the undoped (U xPu x-1)O 2, (U xTh x-1)O 2 and (Pu xTh x-1)O 2 systems where compositions between end members display enhanced diffusivity. Below the superionic transition oxygen diffusivity for the Gd doped systems is orders of magnitude greater compared to their undoped counterparts. But, enhanced diffusivity for doped mixed actinidemore » cation compositions is not observed compared to doped end members. Furthermore, changes in activation energy suggest changes in diffusion regime, which correspond to the creation of thermally activated oxygen defects.« less

Antimicrobial agent-free hybrid cationic starch/sodium alginate polyelectrolyte films for food packaging materials.

PubMed

Şen, Ferhat; Uzunsoy, İrem; Baştürk, Emre; Kahraman, Memet Vezir

2017-08-15

This study aimed to develop polyelectrolyte structured antimicrobial food packaging materials that do not contain any antimicrobial agents. Cationic starch was synthesized and characterized by FT-IR spectroscopy and 1 H NMR spectroscopy. Its nitrogen content was determined by Kjeldahl method. Polyelectrolyte structured antimicrobial food packaging materials were prepared using starch, cationic starch and sodium alginate. Antimicrobial activity of materials was defined by inhibition zone method (disc diffusion method). Thermal stability of samples was evaluated by TGA and DSC. Hydrophobicity of samples was determined by contact angle measurements. Surface morphology of samples was investigated by SEM. Moreover, gel contents of samples were determined. The obtained results prove that produced food packaging materials have good thermal, antimicrobial and surface properties, and they can be used as food packaging material in many industries. Copyright © 2017 Elsevier Ltd. All rights reserved.

Misfit strain driven cation inter-diffusion across an epitaxial multiferroic thin film interface

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

Sankara Rama Krishnan, P. S.; Munroe, Paul; Nagarajan, V.

Cation intermixing at functional oxide interfaces remains a highly controversial area directly relevant to interface-driven nanoelectronic device properties. Here, we systematically explore the cation intermixing in epitaxial (001) oriented multiferroic bismuth ferrite (BFO) grown on a (001) lanthanum aluminate (LAO) substrate. Aberration corrected dedicated scanning transmission electron microscopy and electron energy loss spectroscopy reveal that the interface is not chemically sharp, but with an intermixing of ∼2 nm. The driving force for this process is identified as misfit-driven elastic strain. Landau-Ginzburg-Devonshire-based phenomenological theory was combined with the Sheldon and Shenoy formula in order to understand the influence of boundary conditions andmore » depolarizing fields arising from misfit strain between the LAO substrate and BFO film. The theory predicts the presence of a strong potential gradient at the interface, which decays on moving into the bulk of the film. This potential gradient is significant enough to drive the cation migration across the interface, thereby mitigating the misfit strain. Our results offer new insights on how chemical roughening at oxide interfaces can be effective in stabilizing the structural integrity of the interface without the need for misfit dislocations. These findings offer a general formalism for understanding cation intermixing at highly strained oxide interfaces that are used in nanoelectronic devices.« less

Mechanism of Enhancement of Virus Plaques by Cationic Polymers

PubMed Central

Wallis, Craig; Melnick, Joseph L.

1968-01-01

It has been assumed that plaque enhancement by cationic polymers is due to their binding of sulfated polysaccharides in agar. However, viruses that are enhanced by cationic polymers, diethylaminoethyl-dextran, and protamine were found not to be inhibited by polyanions in agar under the usual overlay conditions. In the case of adenovirus, enhancement by protamine seems to be due to the protamine serving as a source of arginine; enzymes released from the cultured cells digest the protamine and provide a reservoir of arginine for the cells. Other viruses (herpes and echovirus types 3, 4, 5, and 6) known to be susceptible to agar inhibitors were found to be enhanced by cationic polymers even under starch gel and methylcellulose overlays, which are free of polyanions. Since cationic polymers enhance the diffusion of virus through agar or starch gel, plaque enhancement seems to be the result of the gel becoming positively charged so that viruses can move effectively through them. The observation that starch gel and methylcellulose enhance plaque formation with viruses known to be inhibited under agar was also reinvestigated. When the consistency of the agar gel was reduced to the same viscosity of starch gel and methylcellulose overlays, the same plaque counts and sizes were observed under all three overlays. PMID:4986901

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

PubMed

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

2018-04-25

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

NMR Study of Ion Dynamics and Charge Storage in Ionic Liquid Supercapacitors

PubMed Central

2015-01-01

Ionic liquids are emerging as promising new electrolytes for supercapacitors. While their higher operating voltages allow the storage of more energy than organic electrolytes, they cannot currently compete in terms of power performance. More fundamental studies of the mechanism and dynamics of charge storage are required to facilitate the development and application of these materials. Here we demonstrate the application of nuclear magnetic resonance spectroscopy to study the structure and dynamics of ionic liquids confined in porous carbon electrodes. The measurements reveal that ionic liquids spontaneously wet the carbon micropores in the absence of any applied potential and that on application of a potential supercapacitor charging takes place by adsorption of counterions and desorption of co-ions from the pores. We find that adsorption and desorption of anions surprisingly plays a more dominant role than that of the cations. Having elucidated the charging mechanism, we go on to study the factors that affect the rate of ionic diffusion in the carbon micropores in an effort to understand supercapacitor charging dynamics. We show that the line shape of the resonance arising from adsorbed ions is a sensitive probe of their effective diffusion rate, which is found to depend on the ionic liquid studied, as well as the presence of any solvent additives. Taken as whole, our NMR measurements allow us to rationalize the power performances of different electrolytes in supercapacitors. PMID:25973552

Electrostatic coupling between DNA and its counterions modulates the observed translational diffusion coefficients.

PubMed

Stellwagen, Earle; Stellwagen, Nancy C

2015-09-01

Free solution capillary electrophoresis (CE) is a useful technique for measuring the translational diffusion coefficients of charged analytes. The measurements are relatively fast if the polarity of the electric field is reversed to drive the analyte back and forth past the detection window during each run. We have tested the validity of the resulting diffusion coefficients using double-stranded DNA molecules ranging in size from 20 to 960 base pairs as the model system. The diffusion coefficients of small DNAs are equal to values in the literature measured by other techniques. However, the diffusion coefficients of DNA molecules larger than ∼30 base pairs are anomalously high and deviate increasingly from the literature values with increasing DNA molar mass. The anomalously high diffusion coefficients are due to electrostatic coupling between the DNA and its counterions. As a result, the measured diffusion coefficients vary with the diffusion coefficient of the counterion, as well as with cation concentration and electric field strength. These effects can be reduced or eliminated by measuring apparent diffusion coefficients of the DNA at several different electric field strengths and extrapolating the results to zero electric field.

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

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

Li Zhipeng, E-mail: LI.Zhipeng@nims.go.jp; Mori, Toshiyuki; Auchterlonie, Graeme John

2011-09-15

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

In vitro investigation of intestinal transport mechanism of silicon, supplied as orthosilicic acid-vanillin complex.

PubMed

Sergent, Thérèse; Croizet, Karine; Schneider, Yves-Jacques

2017-02-01

Silicon (Si) is one of the most abundant trace elements in the body. Although pharmacokinetics data described its absorption from the diet and its body excretion, the mechanisms involved in the uptake and transport of Si across the gut wall have not been established. Caco-2 cells were used as a well-accepted in vitro model of the human intestinal epithelium to investigate the transport, across the intestinal barrier in both the absorption and excretion directions, of Si supplied as orthosilicic acid stabilized by vanillin complex (OSA-VC). The transport of this species was found proportional to the initial concentration and to the duration of incubation, with absorption and excretion mean rates similar to those of Lucifer yellow, a marker of paracellular diffusion, and increasing in the presence of EGTA, a chelator of divalents cations including calcium. A cellular accumulation of Si, polarized from the apical side of cells, was furthermore detected. These results provide evidence that Si, ingested as a food supplement containing OSA-VC, crosses the intestinal mucosa by passive diffusion via the paracellular pathway through the intercellular tight junctions and accumulates intracellularly, probably by an uptake mechanism of facilitated diffusion. This study can help to further understand the kinetic of absorption of Si. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photoenhanced Attachment for Optical Control of Diffuse Discharges.

DTIC Science & Technology

1987-12-31

17 14 . MONTORING AGNC 14AM & OdRSSii I h e en Controlling Office) IS. SECURITY CLASS. (at Chi* report) Unclassified 15m. OECL ASSI F1CATION... 14 References................................................... 15 Publications................................................. 16...substantial translational energy of the fragments. *: This disposition of energy has important consequences in the 14 4 I . * photochemistry and

Comparison of Minocycline Susceptibility Testing Methods for Carbapenem-Resistant Acinetobacter baumannii.

PubMed

Wang, Peng; Bowler, Sarah L; Kantz, Serena F; Mettus, Roberta T; Guo, Yan; McElheny, Christi L; Doi, Yohei

2016-12-01

Treatment options for infections due to carbapenem-resistant Acinetobacter baumannii are extremely limited. Minocycline is a semisynthetic tetracycline derivative with activity against this pathogen. This study compared susceptibility testing methods that are used in clinical microbiology laboratories (Etest, disk diffusion, and Sensititre broth microdilution methods) for testing of minocycline, tigecycline, and doxycycline against 107 carbapenem-resistant A. baumannii clinical isolates. Susceptibility rates determined with the standard broth microdilution method using cation-adjusted Mueller-Hinton (MH) broth were 77.6% for minocycline and 29% for doxycycline, and 92.5% of isolates had tigecycline MICs of ≤2 μg/ml. Using MH agar from BD and Oxoid, susceptibility rates determined with the Etest method were 67.3% and 52.3% for minocycline, 21.5% and 18.7% for doxycycline, and 71% and 29.9% for tigecycline, respectively. With the disk diffusion method using MH agar from BD and Oxoid, susceptibility rates were 82.2% and 72.9% for minocycline and 34.6% and 34.6% for doxycycline, respectively, and rates of MICs of ≤2 μg/ml were 46.7% and 23.4% for tigecycline. In comparison with the standard broth microdilution results, very major rates were low (∼2.8%) for all three drugs across the methods, but major error rates were higher (∼5.6%), especially with the Etest method. For minocycline, minor error rates ranged from 14% to 37.4%. For tigecycline, minor error rates ranged from 6.5% to 69.2%. The majority of minor errors were due to susceptible results being reported as intermediate. For minocycline susceptibility testing of carbapenem-resistant A. baumannii strains, very major errors are rare, but major and minor errors overcalling strains as intermediate or resistant occur frequently with susceptibility testing methods that are feasible in clinical laboratories. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

A new statistical analysis of rare earth element diffusion data in garnet

NASA Astrophysics Data System (ADS)

Chu, X.; Ague, J. J.

2015-12-01

The incorporation of rare earth elements (REE) in garnet, Sm and Lu in particular, links garnet chemical zoning to absolute age determinations. The application of REE-based geochronology depends critically on the diffusion behaviors of the parent and daughter isotopes. Previous experimental studies on REE diffusion in garnet, however, exhibit significant discrepancies that impact interpretations of garnet Sm/Nd and Lu/Hf ages.We present a new statistical framework to analyze diffusion data for REE using an Arrhenius relationship that accounts for oxygen fugacity, cation radius and garnet unit-cell dimensions [1]. Our approach is based on Bayesian statistics and is implemented by the Markov chain Monte Carlo method. A similar approach has been recently applied to model diffusion of divalent cations in garnet [2]. The analysis incorporates recent data [3] in addition to the data compilation in ref. [1]. We also include the inter-run bias that helps reconcile the discrepancies among data sets. This additional term estimates the reproducibility and other experimental variabilities not explicitly incorporated in the Arrhenius relationship [2] (e.g., compositional dependence [3] and water content).The fitted Arrhenius relationships are consistent with the models in ref. [3], as well as refs. [1]&[4] at high temperatures. Down-temperature extrapolation leads to >0.5 order of magnitude faster diffusion coefficients than in refs. [1]&[4] at <750 °C. The predicted diffusion coefficients are significantly slower than ref. [5]. The fast diffusion [5] was supported by a field test of the Pikwitonei Granulite—the garnet Sm/Nd age postdates the metamorphic peak (750 °C) by ~30 Myr [6], suggesting considerable resetting of the Sm/Nd system during cooling. However, the Pikwitonei Granulite is a recently recognized UHT terrane with peak temperature exceeding 900 °C [7]. The revised closure temperature (~730 °C) is consistent with our new diffusion model.[1] Carlson (2012) Am Mineral 97 1598-1618. [2] Chu & Ague (2015) Contrib Mineral Petrol, in press. [3] Bloch et al. (2015) Contrib Mineral Petrol 169 1-18. [4] Van Orman et al. (2002) Contrib Mineral Petrol 142 416-424. [5] Tirone et al. (2005) GCA 69 2385-2398. [6] Mezger et al. (1992) EPSL 113 397-409. [7] Kooijman et al. (2012) J Metamorph Geol 30 397-412.

Effects of Surfactants on the Improvement of Sludge Dewaterability Using Cationic Flocculants

PubMed Central

Zhai, Jun; Teng, Houkai; Zhao, Chun; Zhao, Chuanliang; Liao, Yong

2014-01-01

The effects of the cationic surfactant (cationic cetyl trimethyl ammonium bromide, CTAB) on the improvement of the sludge dewaterability using the cationic flocculant (cationic polyacrylamide, CPAM) were analyzed. Residual turbidity of supernatant, dry solid (DS) content, extracellular polymeric substances (EPS), specific resistance to filtration (SRF), zeta potential, floc size, and settling rate were investigated, respectively. The result showed that the CTAB positively affected the sludge conditioning and dewatering. Compared to not using surfactant, the DS and the settling rate increased by 8%–21.2% and 9.2%–15.1%, respectively, at 40 mg·L−1 CPAM, 10×10−3 mg·L−1 CTAB, and pH 3. The residual turbidities of the supernatant and SRF were reduced by 14.6%–31.1% and 6.9%–7.8% compared with turbidities and SRF without surfactant. Furthermore, the release of sludge EPS, the increases in size of the sludge flocs, and the sludge settling rate were found to be the main reasons for the CTAB improvement of sludge dewatering performance. PMID:25347394

A Two-Phase Intergrowth in Genthelvite from Mont Saint-Hilaire, Quebec

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

Antao, Sytle M.; Hassan, Ishmael; West Indies)

Synchrotron high-resolution powder X-ray-diffraction (HRPXRD) data and Rietveld structure refinement were used to examine a two-phase intergrowth of genthelvite, ideally Zn{sub 8}[Be{sub 6}Si{sub 6}O{sub 24}]S{sub 2}, from the alkaline intrusive complex at Mont Saint-Hilaire, Quebec, where genthelvite occurs in nepheline syenite pegmatites. The structural parameters obtained for the two phases are slightly different from each other. The unit-cell parameters are 8.119190(7) {angstrom} (51% phase 1) and 8.128914(9) {angstrom} (49% phase 2). The refinement gives the chemical formulae and interstitial M cation in terms of Zn and Mn (the Fe content is practically zero) for the Mn-poor genthelvite phase 1 asmore » (Zn{sub 7.8}Mn{sub 0.2}){Sigma}{sub 8}[Be{sub 6}Si{sub 6}O{sub 24}]S{sub 2}, and the Mn-rich genthelvite phase 2 as (Zn{sub 7.0}Mn{sub 1.0}){Sigma}{sub 8}[Be{sub 6}Si{sub 6}O{sub 24}]S{sub 2}. These formulae are comparable to the Mn-poor and Mn-rich phases obtained by electron-microprobe analysis. The intergrowth indicates that diffusion is absent among the interstitial M cations of similar size (Zn{sup 2+}, Fe{sup 2+} and Mn{sup 2+}). Such intergrowths may form under distinct f(O{sub 2}) conditions and probably low temperature of crystallization that inhibits diffusion of M cations.« less

Anion exchange membranes composed of a poly(2,6-dimethyl-1,4-phenylene oxide) random copolymer functionalized with a bulky phosphonium cation

DOE PAGES

Liu, Ye; Zhang, Bingzi; Kinsinger, Corey L.; ...

2016-01-22

A random copolymer, tris(2,4,6-trimethoxyphenyl) phosphonium functionalized poly(2,6-dimethyl-1,4-phenylene oxide) (PPO-TPQP) was cast from three different solvents: dimethyl sulfoxide (DMSO), ethyl lactate, or a 41:59 vol% mixture of DMSO and ethyl lactate. Solvents were selected via analysis of the Hansen solubility parameters to vary the phase separation of the polymer in the films. An optimized mixture of DMSO and ethyl lactate chosen for film fabrication and this film was contrasted with films cast from the neat constituent solvents. Atomic force microscopy identified domains from nanometer to tens of nanometer sizes, while the light microscopy showed features on the order of micron. SAXSmore » revealed a cation scattering peak with a d-spacing from 7 to 15 Å. Trends in conductivity and water diffusion for the membranes vary depending on the solvent from which they are cast. The mixed solvent cast membrane shows a linear Arrhenius behavior indicating fully dissociated cationic/anionic groups, and has the highest bromide conductivity of 3 mS/cm at 95% RH, 90 °C. The ethyl lactate cast membrane shows a linear Arrhenius relation in conductivity, but a Vogel-Tamman-Fulcher behavior in its water self-diffusion. While water increases bromide dissociation, water and bromide transport in these films seems to be decoupled. Lastly, this is particularly true for the film cast from ethyl lactate.« less

Anion exchange membranes composed of a poly(2,6-dimethyl-1,4-phenylene oxide) random copolymer functionalized with a bulky phosphonium cation

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

Liu, Ye; Zhang, Bingzi; Kinsinger, Corey L.

A random copolymer, tris(2,4,6-trimethoxyphenyl) phosphonium functionalized poly(2,6-dimethyl-1,4-phenylene oxide) (PPO-TPQP) was cast from three different solvents: dimethyl sulfoxide (DMSO), ethyl lactate, or a 41:59 vol% mixture of DMSO and ethyl lactate. Solvents were selected via analysis of the Hansen solubility parameters to vary the phase separation of the polymer in the films. An optimized mixture of DMSO and ethyl lactate chosen for film fabrication and this film was contrasted with films cast from the neat constituent solvents. Atomic force microscopy identified domains from nanometer to tens of nanometer sizes, while the light microscopy showed features on the order of micron. SAXSmore » revealed a cation scattering peak with a d-spacing from 7 to 15 A. Trends in conductivity and water diffusion for the membranes vary depending on the solvent from which they are cast. The mixed solvent cast membrane shows a linear Arrhenius behavior indicating fully dissociated cationic/anionic groups, and has the highest bromide conductivity of 3 mS/cm at 95% RH, 90 degrees C. The ethyl lactate cast membrane shows a linear Arrhenius relation in conductivity, but a Vogel-Tamman-Fulcher behavior in its water self-diffusion. While water increases bromide dissociation, water and bromide transport in these films seems to be decoupled. This is particularly true for the film cast from ethyl lactate.« less

Anion exchange membranes composed of a poly(2,6-dimethyl-1,4-phenylene oxide) random copolymer functionalized with a bulky phosphonium cation

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

Liu, Ye; Zhang, Bingzi; Kinsinger, Corey L.

A random copolymer, tris(2,4,6-trimethoxyphenyl) phosphonium functionalized poly(2,6-dimethyl-1,4-phenylene oxide) (PPO-TPQP) was cast from three different solvents: dimethyl sulfoxide (DMSO), ethyl lactate, or a 41:59 vol% mixture of DMSO and ethyl lactate. Solvents were selected via analysis of the Hansen solubility parameters to vary the phase separation of the polymer in the films. An optimized mixture of DMSO and ethyl lactate chosen for film fabrication and this film was contrasted with films cast from the neat constituent solvents. Atomic force microscopy identified domains from nanometer to tens of nanometer sizes, while the light microscopy showed features on the order of micron. SAXSmore » revealed a cation scattering peak with a d-spacing from 7 to 15 Å. Trends in conductivity and water diffusion for the membranes vary depending on the solvent from which they are cast. The mixed solvent cast membrane shows a linear Arrhenius behavior indicating fully dissociated cationic/anionic groups, and has the highest bromide conductivity of 3 mS/cm at 95% RH, 90 °C. The ethyl lactate cast membrane shows a linear Arrhenius relation in conductivity, but a Vogel-Tamman-Fulcher behavior in its water self-diffusion. While water increases bromide dissociation, water and bromide transport in these films seems to be decoupled. Lastly, this is particularly true for the film cast from ethyl lactate.« less

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.

Correlation of transarterial transport of various dextrans with their physicochemical properties.

PubMed

Elmalak, O; Lovich, M A; Edelman, E

2000-11-01

Local vascular drug delivery provides elevated concentrations of drug in the target tissue while minimizing systemic side effects. To better characterize local pharmacokinetics we examined the arterial transport of locally applied dextran and dextran derivatives in vivo. Using a two-compartment pharmacokinetic model to correct the measured transmural flux of these compounds for systemic redistribution and elimination as delivered from a photopolymerizable hydrogel surrounding rat carotid arteries, we found that the diffusivities and the transendothelial permeabilities were strongly dependent on molecular weight and charge. For neutral dextrans, the effective diffusive resistance in the media increased with molecular weight approximately 4.1-fold between the molecular weights of 10 and 282 kDa. Similarly, endothelial resistance increased 28-fold over the same molecular weight range. The effective medial diffusive resistance was unaffected by cationic charge as such molecules moved identically to neutral compounds, but increased approximately 40% when dextrans were negatively charged. Transendothelial resistance was 20-fold lower for the cationic dextrans, and 11-fold higher for the anionic dextrans, when both were compared to neutral counterparts. These results suggest that, while low molecular weight drugs will rapidly traverse the arterial wall with the endothelium posing a minimal barrier, the reverse is true for high molecular weight agents. With these data, the deposition and distribution of locally released vasotherapeutic compounds might be predicted based upon chemical properties, such as molecular weight and charge.

Theory of the formation of the electric double layer at the ion exchange membrane-solution interface.

PubMed

Moya, A A

2015-02-21

This work aims to extend the study of the formation of the electric double layer at the interface defined by a solution and an ion-exchange membrane on the basis of the Nernst-Planck and Poisson equations, including different values of the counter-ion diffusion coefficient and the dielectric constant in the solution and membrane phases. The network simulation method is used to obtain the time evolution of the electric potential, the displacement electric vector, the electric charge density and the ionic concentrations at the interface between a binary electrolyte solution and a cation-exchange membrane with total co-ion exclusion. The numerical results for the temporal evolution of the interfacial electric potential and the surface electric charge are compared with analytical solutions derived in the limit of the shortest times by considering the Poisson equation for a simple cationic diffusion process. The steady-state results are justified from the Gouy-Chapman theory for the diffuse double layer in the limits of similar and high bathing ionic concentrations with respect to the fixed-charge concentration inside the membrane. Interesting new physical insights arise from the interpretation of the process of the formation of the electric double layer at the ion exchange membrane-solution interface on the basis of a membrane model with total co-ion exclusion.

Acceleration of chemical weathering related to intensive agriculture: evidence from groundwater dating

NASA Astrophysics Data System (ADS)

Aquilina, Luc; Marçais, Jean; de Dreuzy, Jean-Raynald; Labasque, Thierry; Abbott, Ben; Vergnaud, Virginie; Walter, Christian; Viville, Daniel; Chabaux, François; Pinay, Gilles

2017-04-01

Agricultural pollution is a matter of political and scientific concern throughout the world. Intensive agriculture can cause nutrient contamination of groundwater and surface water. Nutrient pollution causes eutrophication in freshwater and estuarine ecosystems. A secondary effect of agricultural intensification is river acidification. Oxidation of chemical fertilizers such as ammonium (NH4+) to nitrate (NO3-) produces H+ ions that cause leaching of cations from soil and deeper material to maintain charge balance. Monitoring of various rivers in Brittany (western France) revealed that agriculture intensification has led to increased cation export starting in the 1980s. From the cation ratios, we deduced that cation increase comes approximately equally from dissolution of carbonate added to soil (liming practices) and silicate dissolution. Cation export represented about 30% of the soil cation exchange potential. If compensated by liming, it may constitute a non-negligible source to atmospheric CO2 (Aquilina et al., 2012). We further investigated the potential for silicate dissolution through the use of groundwater dating in various sites of Brittany. Coupling chemical analyses to groundwater ages in a large range of aquifers and a large range of depths (down to 110m) allowed us to reconstruct a chronicle for the last 50 yrs of the cation concentrations of groundwater. It clearly shows a contemporaneous increase in sodium and nitrate and a decrease in calcium, with the most dramatic changes occurring during the 70s and 80s. Using groundwater dating, we were also able to determine a silica production geochronometer. A tight and linear relationship between silica concentration and groundwater age (Figure) was observed and allowed a production rate in groundwater to be determined. Except for short residence-times (Kerrien), the silica production rate for different granitic catchments was consistent, ranging from 0.3 to 0.4 mg.L-1.yr-1. To assess the role of anthropogenic activity in silica production rate, we compared production rates from Brittany with catchments in the Vosges Mountains, a relatively pristine area. Dissolution rates were much higher in the Brittany catchments, indicating the effect of human activities on chemical weathering and cation export at the catchment scale. Aquilina L. et al., 2012 - Long-term effects of high nitrogen loads on cation and carbon riverine export in agricultural catchments. Env. Sci & Technology 46-17, 9447-9455..

Investigation of Oxygen Diffusion in Irradiated UO2 with MD Simulation

NASA Astrophysics Data System (ADS)

Günay, Seçkin D.

2016-11-01

In this study, irradiated UO2 is analyzed by atomistic simulation method to obtain diffusion coefficient of oxygen ions. For this purpose, a couple of molecular dynamics (MD) supercells containing Frenkel, Schottky, vacancy and interstitial types for both anion and cation defects is constructed individually. Each of their contribution is used to calculate the total oxygen diffusion for both intrinsic and extrinsic ranges. The results display that irradiation-induced defects contribute the most to the overall oxygen diffusion at temperatures below 800-1,200 K. This result is quite sensible because experimental data shows that, from room temperature to about 1,500 K, irradiation-induced swelling decreases and irradiated UO2 lattice parameter is gradually recovered because defects annihilate each other. Another point is that, concentration of defects enhances the irradiation-induced oxygen diffusion. Irradiation type also has the similar effect, namely oxygen diffusion in crystals irradiated with α-particles is more than the crystals irradiated with neutrons. Dynamic Frenkel defects dominate the oxygen diffusion data above 1,500—1,800 K. In all these temperature ranges, thermally induced Frenkel defects make no significant contribution to overall oxygen diffusion.

Modeling transport kinetics in clinoptilolite-phosphate rock systems

NASA Technical Reports Server (NTRS)

Allen, E. R.; Ming, D. W.; Hossner, L. R.; Henninger, D. L.

1995-01-01

Nutrient release in clinoptilolite-phosphate rock (Cp-PR) systems occurs through dissolution and cation-exchange reactions. Investigating the kinetics of these reactions expands our understanding of nutrient release processes. Research was conducted to model transport kinetics of nutrient release in Cp-PR systems. The objectives were to identify empirical models that best describe NH4, K, and P release and define diffusion-controlling processes. Materials included a Texas clinoptilolite (Cp) and North Carolina phosphate rock (PR). A continuous-flow thin-disk technique was used. Models evaluated included zero order, first order, second order, parabolic diffusion, simplified Elovich, Elovich, and power function. The power-function, Elovich, and parabolic-diffusion models adequately described NH4, K, and P release. The power-function model was preferred because of its simplicity. Models indicated nutrient release was diffusion controlled. Primary transport processes controlling nutrient release for the time span observed were probably the result of a combination of several interacting transport mechanisms.

Does the cation really matter? The effect of modifying an ionic liquid cation on an SN2 process.

PubMed

Tanner, Eden E L; Yau, Hon Man; Hawker, Rebecca R; Croft, Anna K; Harper, Jason B

2013-09-28

The rate of reaction of a Menschutkin process in a range of ionic liquids with different cations was investigated, with temperature-dependent kinetic data giving access to activation parameters for the process in each solvent. These data, along with molecular dynamics simulations, demonstrate the importance of accessibility of the charged centre on the cation and that the key interactions are of a generalised electrostatic nature.

Diffusion modelling of metamorphic layered coronas with stability criterion and consideration of affinity

NASA Astrophysics Data System (ADS)

Ashworth, J. R.; Sheplev, V. S.

1997-09-01

Layered coronas between two reactant minerals can, in many cases, be attributed to diffusion-controlled growth with local equilibrium. This paper clarifies and unifies the previous approaches of various authors to the simplest form of modelling, which uses no assumed values for thermochemical quantities. A realistic overall reaction must be estimated from measured overall proportions of minerals and their major element compositions. Modelling is not restricted to a particular number of components S, relative to the number of phases Φ. IfΦ > S + 1, the overall reaction is a combination of simultaneous reactions. The stepwise method, solving for the local reaction at each boundary in turn, is extended to allow for recurrence of a mineral (its presence in two parts of the layer structure separated by a gap). The equations are also given in matrix form. A thermodynamic stability criterion is derived, determining which layer sequence is truly stable if several are computable from the same inputs. A layer structure satisfying the stability criterion has greater growth rate (and greater rate of entropy production) than the other computable layer sequences. This criterion of greatest entropy production is distinct from Prigogine's theorem of minimum entropy production, which distinguishes the stationary or quasi-stationary state from other states of the same layer sequence. The criterion leads to modification of previous results for coronas comprising hornblende, spinel, and orthopyroxene between olivine (Ol) and plagioclase (Pl). The outcome supports the previous inference that Si, and particularly Al, commonly behave as immobile relative to other cation-forming major elements. The affinity (-ΔG) of a corona-forming reaction is estimated, using previous estimates of diffusion coefficient and the duration t of reaction, together with a new model quantity (-ΔG) *. For an example of the Ol + Pl reaction, a rough calculation gives (-ΔG) > 1.7RT (per mole of P1 consumed, based on a 24-oxygen formula for Pl). At 600-700°C, this represents (-ΔG) > 10kJ mol -1 and departure from equilibrium temperature by at least ˜ 100°C. The lower end of this range is petrologically reasonable and, for t < 100Ma, corresponds to a Fick's-law diffusion coefficient for Al, DAl > 10 -25m 2s -1, larger than expected for lattice diffusion but consistent with fluid-absent grain-boundary diffusion and small concentration gradients.

Transports of ionic liquids in ionic polymer conductor network composite actuators

NASA Astrophysics Data System (ADS)

Liu, Yang; Liu, Sheng; Lin, Junhong; Wang, Dong; Jain, Vaibhav; Montazami, Reza; Heflin, James R.; Li, Jing; Madsen, Louis; Zhang, Q. M.

2010-04-01

We investigate the influence of ionic liquids on the electromechanical performance of Ionic Polymer Conductor Network Composite (IPCNC) bending actuators. Two imidazolium ionic liquids (ILs) with one cation, which is 1-ethyl-3- methylimidazolium ([EMI+]), and two different anions, which are tetrafluoroborate ([BF4-]) and trifluoromethanesulfonate ([Tf-]), are chosen for the study. By combining the time domain electric and electromechanical responses, we developed a new model that describes the ion transports in IPCNC actuators. The time constant of excess cation and anion migration in various composite electrodes are deduced: 6s and 25s in RuO2/Nafion; 7.9s and 36.3s in RuO2/Aquivion; 4.8s and 53s in Au/PAH, respectively. NMR is also applied to provide quantitative measures of self-diffusion coefficients independently for IL anions and cations both in pure ILs and in ILs absorved into ionomers. All the results indicate that the motion of cation, in the studied pure ionic liquids, polymer matrix and conductor network composites, is faster than that of anion. Moreover, the CNC morphology is playing a crucial role in determining the ion transport in the porous electrodes.

Flux Decoupling and Chemical Diffusion in Redox Dynamics in Aluminosilicate Melts and Glasses (Invited)

NASA Astrophysics Data System (ADS)

Cooper, R. F.

2010-12-01

Measurements of redox dynamics in silicate melts and glasses suggest that, for many compositions and for many external environments, the reaction proceeds and is rate-limited by the diffusive flux of divalent-cation network modifiers. Application of ion-backscattering spectrometry either (i) on oxidized or reduced melts (subsequently quenched before analysis) or (ii) on similarly reacted glasses, both of basalt-composition polymerization, demonstrates that the network modifiers move relative to the (first-order-rigid) aluminosilicate network. Thus, the textures associated with such reactions are often surprising, and frequently include metastable or unstable phases and/or spatial compositional differences. This response is only possible if the motion of cations can be decoupled from that of anions. In many cases, decoupling is accomplished by the presence in the melt/glass of transition-metal cations, whose heterovalency creates distortions in the electronic band structure resulting in electronic defects: electron “holes” in the valence band or electrons in the conduction band. (The prevalence of holes or electrons being a function of bulk chemistry and oxygen activity.) These electronic species make the melt/glass a “defect semiconductor.” Because (a) the critical issue in reaction dynamics is the transport coefficient (the product of species mobility and species concentration) and (b) the electronic species are many orders of magnitude more mobile than are the ions, very low concentrations of transition-metal ions are required for flux decoupling. For example, 0.04 at% Fe keeps a magnesium aluminosilicate melt/glass a defect semiconductor down to 800°C [Cook & Cooper, 2000]. Depending on composition, high-temperature melts can see ion species having a high-enough transport coefficient to allow decoupling, e.g., alkali cations in a basaltic melt [e.g., Pommier et al., 2010]. In this presentation, these ideas will be illustrated by examining redox dynamics in basaltic melts [e.g., Burgess et al., 2010; Cooper et al., 2010] and the reaction of magnesium aluminosilicate melts (transition-metal-ion-free and -doped) with liquid bronze (Cu-Sn alloy) [Pettersen et al., 2008], the latter demonstrating the importance of heterovalency in silicon [e.g., Borman et al., 1991] in effecting the reaction dynamics and resultant texture. Borman, V.D. et al. (1991) Phys. Rev. Lett. 67:2387-2390. Burgess, K. et al. (2010) Geochem. Geophys. Geosyst. 11:in press. Cook, G.B., and R.F. Cooper (2000) Am. Mineral. 85:397-406. Cooper, R.F. et al. (2010) Am. Mineral. 95:810-824. Pettersen, C., and R.F. Cooper (2008) J. Non-Crys. Solids 354:3194-3206. Pommier, A. et al. (2010) Geochim. Cosmochim. Acta 74:1653-1671.

Illitization of Potassium, Cesium, and Ammonium Exchanged Smectite

NASA Astrophysics Data System (ADS)

Mills, M. M.; Wang, Y.; Payne, C.; Sanchez, A. C.; Boisvert, L.; Matteo, E. N.

2017-12-01

Bentonite clay is a primary choice for engineered barrier systems within geologic repositories for disposal of radioactive wastes due to its low permeability at saturated states, warranting diffusion as the dominant transport mechanism, and large swelling pressures that promote sealing. In order to predict how well the barrier will function over time at repository relevant temperatures, it is important to understand thermal alteration effects on montmorillonite, better known as smectite, a main constituent of bentonite. One type of thermal alteration is the conversion to illite, when exposed to elevated temperatures and a sufficient amount of potassium ions, thereby weakening barrier functions. To facilitate the conversion of smectite to illite and examine the influence of interlayer cations, illitization experiments on cation exchanged smectite were performed within hydrothermal reaction vessels over one week timescales. The <2um fraction of a Na-rich smectite clay was first exchanged with 1M Cs, K, and NH4 salt solutions and further exposed to hydrous pyrolysis using a 1M KCl solution with various solid to liquid ratios at 200°C. Multiple analysis techniques were used to characterize the altered clay and identify extent of conversion, such as XRD, cation exchange capacity, and morphology changes by SEM. The pore-water chemistry was also analyzed by ICP-OES to detect any dissolved products and silica content. Results suggest the conversion rate is relatively fast, occurring within days, and is dependent on not only the amount of K, but also dissolved silica concentration related to total solid in solution. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia LLC, a wholly owned subsidiary of Honeywell International Inc. for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA0003525. SAND2017-7856A

FACTORS AFFECTING THE ELECTROPHILICITY AND NUCLEOPHILICITY OF REAGENTS.

DTIC Science & Technology

The apparent simplicity of the reactions of Malachite Green cation (bis-(p-dimethylaminophenyl), phenylmethyl cation) with nucleophilic reagents...initiated to study the rates of the reactions of a series of Malachite Green cations with a number of nucleophilies in several dipolar aprotic solvents, and the same reactions in water for comparison. (Author)

Modeling of bleach plant washer mineral scale

Treesearch

Alan Rudie; Peter Hart

2004-01-01

One of the more common areas of mineral scale formation in bleach plants is on washer face wires and the extraction rings of diffusion washers. Whereas most scale problems can be understood as a mixing of two streams that increase the concentrations of anions and cations and exceed a solubility product, washer problems are often more difficult to understand. The...

Gating current studies reveal both intra- and extracellular cation modulation of K+ channel deactivation

PubMed Central

Wang, Zhuren; Zhang, Xue; Fedida, David

1999-01-01

The presence of permeant ions can modulate the rate of gating charge return in wild-type human heart K+ (hKv1.5) channels. Here we employ gating current measurements in a non-conducting mutant, W472F, of the hKv1.5 channel to investigate how different cations can modulate charge return and whether the actions can be specifically localized at the internal as well as the external mouth of the channel pore. Intracellular cations were effective at accelerating charge return in the sequence Cs+ > Rb+ > K+ > Na+ > NMG+. Extracellular cations accelerated charge return with the selectivity sequence Cs+ > Rb+ > Na+ = NMG+. Intracellular and extracellular cation actions were of relatively low affinity. The Kd for preventing slowing of the time constant of the off-gating current decay (τoff) was 20.2 mM for intracellular Cs+ (Csi+) and 358 mM for extracellular Cs+ (Cso+). Both intracellular and extracellular cations can regulate the rate of charge return during deactivation of hKv1.5, but intracellular cations are more effective. We suggest that ion crystal radius is an important determinant of this action, with larger ions preventing slowing more effectively. Important parallels exist with cation-dependent modulation of slow inactivation of ionic currents in this channel. However, further experiments are required to understand the exact relationship between acceleration of charge return and the slowing of inactivation of ionic currents by cations. PMID:10050001

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

PubMed Central

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

2015-01-01

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

Application of SR Methods for the Study of Nanocomposite Materials for Hydrogen Energy

NASA Astrophysics Data System (ADS)

Sadykov, V. A.; Pavlova, S. N.; Vinokurov, Z. S.; Shmakov, A. N.; Eremeev, N. F.; Fedorova, Yu. E.; Yakimchuk, E. P.; Kriventsov, V. V.; Bolotov, V. A.; Tanashev, Yu. Yu.; Sadovskaya, E. M.; Cherepanova, S. V.; Zolotarev, K. V.

This work summarizes results of synchrotron radiation (SR) studies of the real/defect structure of nanocrystalline/nanocomposite oxide materials, which determines their functional properties in hydrogen energy field as catalysts and mixed ionic electronic conductors (cathodes and anodes of solid oxide fuel cells, oxygen separation membranes). For nanocrystalline ceria-zirconia mixed oxide prepared via modified Pechini route using ethanol solution of reagents, a high spatial uniformity of cations distribution between domains along with the oxygen sublattice deficiency revealed by full-profile Rietveld refinement of SR diffraction data provide structure disordering enhancing oxygen mobility. For PrNi0.5Co0.5O3-δ - Ce0.9Y0.1O2-δ nanocomposite extensive transfer of Pr cations into fluorite domains generates a new path of fast oxygen diffusion along chains of Pr3+ - Pr4+ cations as directly proved by analysis of the unit cell relaxation after changing pO2 in perfect agreement with data obtained by oxygen isotope heteroexchange.

Synthesis and characterization of heterometallic uranyl pyridinedicarboxylate compounds

NASA Astrophysics Data System (ADS)

Jayasinghe, Ashini S.; Payne, Maurice K.; Forbes, Tori Z.

2017-10-01

The incorporation of transition metals into hybrid uranyl materials can result in more diverse structural topologies and variations in physical and chemical properties. To explore the impact of transition metals on the uranyl cation, five uranium containing bimetallic chain compounds, [(UO2)M(PDC)2(H2O)4]·4(H2O) (PDC = 2,6 pyridinedicarboxylate; M = Ni2+, Co2+, Fe2+, Zn2+, and Cu2+) were synthesized by evaporation of aqueous solutions at room temperature. The uranyl cation is complex by two PDC ligands and the transition metal cations bond to the complex to form a one-dimensional chain topology. The presence of the transition metal leads to the presence of a stronger uranyl oxo bonds as shown by the single-crystal X-ray diffraction data and the Raman spectra. Solid state diffuse reflectance UV/Visible spectra confirmed the presence of the transition metals in the structure by the broad bands that appeared at relevant wavelengths.

Diffusion of hydrous species in model basaltic melt

NASA Astrophysics Data System (ADS)

Zhang, Li; Guo, Xuan; Wang, Qinxia; Ding, Jiale; Ni, Huaiwei

2017-10-01

Water diffusion in Fe-free model basaltic melt with up to 2 wt% H2O was investigated at 1658-1846 K and 1 GPa in piston-cylinder apparatus using both hydration and diffusion couple techniques. Diffusion profiles measured by FTIR are consistent with a model in which both molecular H2O (H2Om) and hydroxyl (OH) contribute to water diffusion. OH diffusivity is roughly 13% of H2Om diffusivity, showing little dependence on temperature or water concentration. Water diffusion is dominated by the motion of OH until total H2O (H2Ot) concentration reaches 1 wt%. The dependence of apparent H2Ot diffusivity on H2Ot concentration appears to be overestimated by a previous study on MORB melt, but H2Ot diffusivity at 1 wt% H2Ot in basaltic melt is still greater than those in rhyolitic to andesitic melts. The appreciable contribution of OH to water diffusion in basaltic melt can be explained by enhanced mobility of OH, probably associated with the development of free hydroxyl bonded with network-modifying cations, as well as higher OH concentration. Calculation based on the Nernst-Einstein equation demonstrates that OH may serve as an effective charge carrier in hydrous basaltic melt, which could partly account for the previously observed strong influence of water on electrical conductivity of basaltic melt.

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

PubMed

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

2016-04-11

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

Solvothermal synthesis of Mg-doped Li2FeSiO4/C nanocomposite cathode materials for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Kumar, Ajay; Jayakumar, O. D.; Naik, V. M.; Nazri, G. A.; Naik, R.

Lithium transition metal orthosilicates, such as Li2FeSiO4 and Li2MnSiO4, as cathode material have attracted much attention lately due to their high theoretical capacity ( 330 mAh/g), low cost, and environmental friendliness. However, they suffer from poor electronic conductivity and slow lithium ion diffusion in the solid phase. Several cation-doped orthosilicates have been studied to improve their electrochemical performance. We have synthesized partially Mg-substituted Li2Mgx Fe1-x SiO4-C, (x = 0.0, 0.01, 0.02, and 0.04) nano-composites by solvothermal method followed by annealing at 600oC in argon flow. The structure and morphology of the composites were characterized by XRD, SEM and TEM. The surface area and pore size distribution were measured by using N2 adsorption/desorption curves. The electrochemical performance of the Li2MgxFe1-x SiO4-C composites was evaluated by Galvanostatic cycling against metallic lithium anode, electrochemical impedance spectroscopy, and cyclic voltammetry. Li2Mg0.01Fe0.99SiO4-C sample shows a capacity of 278 mAh/g (at C/30 rate in the 1.5-4.6 V voltage window) with an excellent rate capability and stability, compared to the other samples. We attribute this observation to its higher surface area, enhanced electronic conductivity and higher lithium ion diffusion coefficient.

Synthesis of nanopowders of the aluminum-substituted lanthanum gallate solid electrolyte by mechanochemical route

NASA Astrophysics Data System (ADS)

Domingues, Eddy M.; Gonçalves, Priscila; Figueiredo, Filipe M.

2012-07-01

The room temperature mechanosynthesis of La1-xSrxGa1-y-zMgyAlzO3-δ nanopowders is successfully demonstrated for a broad compositional range (x ≤ 0.1; y ≤ 0.2, z ≤ 0.4) by resorting to a nearly amorphous alumina precursor with enhanced reactivity. It is shown that ceramics with one single phase and free from open porosity can be obtained by sintering these nanopowders at 1350-1450 °C. Microstructural data show that the substitution of Ga by Al hinders densification and decreases the grain size of ceramics. This is explained assuming the segregation of aluminum cations to the grain boundaries as a result of the decrease of the cationic diffusion coefficients.

Characterization, production, and purification of carnocin H, a bacteriocin produced by Carnobacterium 377.

PubMed

Blom, H; Katla, T; Nissen, H; Holo, H

2001-10-01

Carnocin H, a bacteriocin produced by a Carnobacterium sp., inhibited lactic acid bacteria, clostridia, enterococci, and some Staphylococcus aureus strains. Some strains of Listeria and Pediococcus were also sensitive to carnocin H. The bacteriocin was produced during the late stationary growth phase. Carnocin H was purified by cation exchange chromatography and reverse phase chromatography. Amino acid sequence and composition indicate that carnocin H is a novel bacteriocin belonging to the class II bacteriocins. The bacteriocin consists of approximately 75 amino acid residues with a highly cationic N-terminal containing six succeeding lysines. Activity, as measured by agar diffusion zones, was reduced at increased pH values, levels of indicator bacteria, NaCl, agar, and soy oil.

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

PubMed

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

2015-01-01

Valuable techniques to measure effective diffusion coefficients in porous media are an indispensable prerequisite for a proper understanding of the migration of chemical-toxic and radioactive micropollutants in the subsurface and geosphere. The present article discusses possible pitfalls and difficulties in the classical through-diffusion technique applied to situations where large diffusive fluxes of cations in compacted clay minerals or clay rocks occur. The results obtained from a benchmark study, in which the diffusion of (85)Sr(2+) tracer in compacted illite has been studied using different experimental techniques, are presented. It is shown that these techniques may yield valuable results provided that an appropriate model is used for numerical simulations. It is further shown that effective diffusion coefficients may be systematically underestimated when the concentration at the downstream boundary is not taken adequately into account in modelling, even for very low concentrations. A criterion is derived for quasi steady-state situations, by which it can be decided whether the simplifying assumption of a zero-concentration at the downstream boundary in through-diffusion is justified or not. The application of the criterion requires, however, knowledge of the effective diffusion coefficient of the clay sample. Such knowledge is often absent or only approximately available during the planning phase of a diffusion experiment. Copyright © 2015 Elsevier B.V. All rights reserved.

High-pressure nuclear magnetic resonance studies of fuel cell membranes

NASA Astrophysics Data System (ADS)

Mananga, Eugene Stephane

This thesis focuses on the use of high pressure NMR to study transport properties in electrolyte membranes used for fuel cells. The main concern is in studying the self-diffusion coefficients of ions and molecules in membranes and solutions, which can be used to characterize electrolytes in fuel cells. For this purpose, a high-pressure fringe field NMR method to study transport properties in material systems useful for fuel cell and battery electrolytes, was designed, developed, and implemented. In this investigation, pressure is the thermodynamic variable to obtain additional information about the ionic transport process, which could yield the crucial parameter, activation volume. Most of the work involves proton NMR, with additional investigations of others nuclei, such as fluorine, phosphorus and lithium. Using the FFG method, two fuel cell membrane types (NAFION-117, SPTES), and different dilutions of phosphoric acid were investigated, as was LiTf salt in Diglyme solution, which is used as a lithium battery electrolyte. In addition to high-pressure NMR diffusion measurements carried out in the fringe field gradient for the investigation of SPTES, pulse field gradient spin echo NMR was also used to characterize the water diffusion, in addition to measuring diffusion rates as a function of temperature. This second method allows us to measure distinct diffusion coefficients in cases where the different nuclear (proton) environments can be resolved in the NMR spectrum. Polymer electrolyte systems, in which the mobility of both cations and anions is probed by NMR self-diffusion measurements using standard pulsed field gradient methods and static gradient measurements as a function of applied hydrostatic pressure, were also investigated. The material investigated is the low molecular weight liquid diglyme/LiCF3SO3 (LiTf) complexes which can be used as electrolytes in lithium batteries. Finally, high-pressure diffusion coefficient measurements of phosphoric acid in water at different concentrations: proton (1H) and phosphorus (31P) nuclei have been performed using the static field gradient spin-echo nuclear magnetic resonance. This study is expected to be helpful in improving the understanding of phosphoric acid fuel cell technology.

Enhanced stability and thermoelectric figure-of-merit in copper selenide by lithium doping

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

Kang, Stephen Dongmin; Pöhls, Jan-Hendrik; Aydemir, Umut

Superionic thermoelectric materials have been shown to have high figure-of-merits, leading to expectations for efficient high-temperature thermoelectric generators. These compounds exhibit extremely high cation diffusivity, comparable to that of a liquid, which is believed to be associated with the low thermal conductivity that makes superionic materials good for thermoelectrics. However, the superionic behavior causes cation migration that leads to device deterioration, being the main obstacle for practical applications. It has been reported that lithium doping in superionic Cu2-xSe leads to suppression of the Cu ion diffusivity, but whether the material will retain the promising thermoelectric properties had not yet beenmore » investigated. Here, we report a maximum zT>1.4 from Li0.09Cu1.9Se, which is higher than what we find in the undoped samples. The high temperature effective weighted mobility of the doped sample is found higher than Cu2-xSe, while the lattice thermal conductivity remains similar. We find signatures of suppressed bipolar conduction due to an enlarged band gap. Our findings set forth a possible route for tuning the stability of superionic thermoelectric materials.« less

Reversed nanoscale Kirkendall effect in Au–InAs hybrid nanoparticles

DOE PAGES

Liu, Jing; Amit, Yorai; Li, Yuanyuan; ...

2016-10-10

Metal–semiconductor hybrid nanoparticles (NPs) offer interesting synergistic properties, leading to unique behaviors that have already been exploited in photocatalysis, electrical, and optoelectronic applications. A fundamental aspect in the synthesis of metal–semiconductor hybrid NPs is the possible diffusion of the metal species through the semiconductor lattice. The importance of understanding and controlling the co-diffusion of different constituents is demonstrated in the synthesis of various hollow-structured NPs via the Kirkendall effect. Here, we used a postsynthesis room-temperature reaction between AuCl 3 and InAs nanocrystals (NCs) to form metal–semiconductor core–shell hybrid NPs through the “reversed Kirkendall effect”. In the presented system, the diffusionmore » rate of the inward diffusing species (Au) is faster than that of the outward diffusing species (InAs), which results in the formation of a crystalline metallic Au core surrounded by an amorphous, oxidized InAs shell containing nanoscale voids. We used time-resolved X-ray absorption fine-structure (XAFS) spectroscopy to monitor the diffusion process and found that both the size of the Au core and the extent of the disorder of the InAs shell depend strongly on the Au-to-NC ratio. We have determined, based on multielement fit analysis, that Au diffuses into the NC via the kick-out mechanism, substituting for In host atoms; this compromises the structural stability of the lattice and triggers the formation of In–O bonds. These bonds were used as markers to follow the diffusion process and indicate the extent of degradation of the NC lattice. Time-resolved X-ray diffraction (XRD) was used to measure the changes in the crystal structures of InAs and the nanoscale Au phases. By combining the results of XAFS, XRD, and electron microscopy, we correlated the changes in the local structure around Au, As, and In atoms and the changes in the overall InAs crystal structure. This correlative analysis revealed a co-dependence of different structural consequences when introducing Au into the InAs NCs. As a result this study of diffusion effects in nanocrystals has relevance to powerful concepts in solid-state nanochemistry related to processes of cation exchange, doping reactions, and diffusion mechanisms.« less

Reversed Nanoscale Kirkendall Effect in Au–InAs Hybrid Nanoparticles

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

Liu, Jing; Amit, Yorai; Li, Yuanyuan

2016-11-08

Metal–semiconductor hybrid nanoparticles (NPs) offer interesting synergistic properties, leading to unique behaviors that have already been exploited in photocatalysis, electrical, and optoelectronic applications. A fundamental aspect in the synthesis of metal–semiconductor hybrid NPs is the possible diffusion of the metal species through the semiconductor lattice. The importance of understanding and controlling the co-diffusion of different constituents is demonstrated in the synthesis of various hollow-structured NPs via the Kirkendall effect. Here, we used a postsynthesis room-temperature reaction between AuCl 3 and InAs nanocrystals (NCs) to form metal–semiconductor core–shell hybrid NPs through the “reversed Kirkendall effect”. In the presented system, the diffusionmore » rate of the inward diffusing species (Au) is faster than that of the outward diffusing species (InAs), which results in the formation of a crystalline metallic Au core surrounded by an amorphous, oxidized InAs shell containing nanoscale voids. We used time-resolved X-ray absorption fine-structure (XAFS) spectroscopy to monitor the diffusion process and found that both the size of the Au core and the extent of the disorder of the InAs shell depend strongly on the Au-to-NC ratio. We have determined, based on multielement fit analysis, that Au diffuses into the NC via the kick-out mechanism, substituting for In host atoms; this compromises the structural stability of the lattice and triggers the formation of In–O bonds. These bonds were used as markers to follow the diffusion process and indicate the extent of degradation of the NC lattice. Time-resolved X-ray diffraction (XRD) was used to measure the changes in the crystal structures of InAs and the nanoscale Au phases. By combining the results of XAFS, XRD, and electron microscopy, we correlated the changes in the local structure around Au, As, and In atoms and the changes in the overall InAs crystal structure. This correlative analysis revealed a co-dependence of different structural consequences when introducing Au into the InAs NCs. Therefore, this study of diffusion effects in nanocrystals has relevance to powerful concepts in solid-state nanochemistry related to processes of cation exchange, doping reactions, and diffusion mechanisms.« less

The load and release characteristics on a strong cationic ion-exchange fiber: kinetics, thermodynamics, and influences.

PubMed

Yuan, Jing; Gao, Yanan; Wang, Xinyu; Liu, Hongzhuo; Che, Xin; Xu, Lu; Yang, Yang; Wang, Qifang; Wang, Yan; Li, Sanming

2014-01-01

Ion-exchange fibers were different from conventional ion-exchange resins in their non-cross-linked structure. The exchange was located on the surface of the framework, and the transport resistance reduced significantly, which might mean that the exchange is controlled by an ionic reaction instead of diffusion. Therefore, this work aimed to investigate the load and release characteristics of five model drugs with the strong cationic ion-exchange fiber ZB-1. Drugs were loaded using a batch process and released in United States Pharmacopoeia (USP) dissolution apparatus 2. Opposing exchange kinetics, suitable for the special structure of the fiber, were developed for describing the exchange process with the help of thermodynamics, which illustrated that the load was controlled by an ionic reaction. The molecular weight was the most important factor to influence the drug load and release rate. Strong alkalinity and rings in the molecular structures made the affinity between the drug and fiber strong, while logP did not cause any profound differences. The drug-fiber complexes exhibited sustained release. Different kinds and concentrations of counter ions or different amounts of drug-fiber complexes in the release medium affected the release behavior, while the pH value was independent of it. The groundwork for in-depth exploration and further application of ion-exchange fibers has been laid.

The load and release characteristics on a strong cationic ion-exchange fiber: kinetics, thermodynamics, and influences

PubMed Central

Yuan, Jing; Gao, Yanan; Wang, Xinyu; Liu, Hongzhuo; Che, Xin; Xu, Lu; Yang, Yang; Wang, Qifang; Wang, Yan; Li, Sanming

2014-01-01

Ion-exchange fibers were different from conventional ion-exchange resins in their non-cross-linked structure. The exchange was located on the surface of the framework, and the transport resistance reduced significantly, which might mean that the exchange is controlled by an ionic reaction instead of diffusion. Therefore, this work aimed to investigate the load and release characteristics of five model drugs with the strong cationic ion-exchange fiber ZB-1. Drugs were loaded using a batch process and released in United States Pharmacopoeia (USP) dissolution apparatus 2. Opposing exchange kinetics, suitable for the special structure of the fiber, were developed for describing the exchange process with the help of thermodynamics, which illustrated that the load was controlled by an ionic reaction. The molecular weight was the most important factor to influence the drug load and release rate. Strong alkalinity and rings in the molecular structures made the affinity between the drug and fiber strong, while logP did not cause any profound differences. The drug–fiber complexes exhibited sustained release. Different kinds and concentrations of counter ions or different amounts of drug–fiber complexes in the release medium affected the release behavior, while the pH value was independent of it. The groundwork for in-depth exploration and further application of ion-exchange fibers has been laid. PMID:25114504

Diffusion kinetics of the ion exchange of benzocaine on sulfocationites

NASA Astrophysics Data System (ADS)

Al'tshuler, O. G.; Shkurenko, G. Yu.; Gorlov, A. A.; Al'tshuler, G. N.

2016-06-01

The theory of the ion exchange kinetics on strong acid cationites with the participation of weak electrolytes is discussed. The kinetics of desorption of benzocaine in the protonated and molecular forms from strong acid cationites, sulfonated polycalixarene, and KU-23 30/100 sulfocationite, is studied experimentally. It is shown that the flow of protonated benzocaine from cationite upon desorption proceeding by the ion-exchange mechanism is more intense than upon desorption of nonionized benzocaine molecules. It is established that the diffusion coefficient of benzocaine cations is (1.21 ± 0.23) × 10-12 m2/s in KU-23 30/100 sulfocation and (0.65 ± 0.06) × 10-13 m2/s in sulfonated polycalixarene, while the diffusion coefficient of benzocaine molecules is (0.65 ± 0.15) × 10-14 m2/s in sulfonated polycalixarene.

Molecular dynamics computer simulation of permeation in solids

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

Pohl, P.I.; Heffelfinger, G.S.; Fisler, D.K.

1997-12-31

In this work the authors simulate permeation of gases and cations in solid models using molecular mechanics and a dual control volume grand canonical molecular dynamics technique. The molecular sieving nature of microporous zeolites are discussed and compared with that for amorphous silica made by sol-gel methods. One mesoporous and one microporous membrane model are tested with Lennard-Jones gases corresponding to He, H{sub 2}, Ar and CH{sub 4}. The mesoporous membrane model clearly follows a Knudsen diffusion mechanism, while the microporous model having a hard-sphere cutoff pore diameter of {approximately}3.4 {angstrom} demonstrates molecular sieving of the methane ({sigma} = 3.8more » {angstrom}) but anomalous behavior for Ar ({sigma} = 3.4 {angstrom}). Preliminary results of Ca{sup +} diffusion in calcite and He/H{sub 2} diffusion in polyisobutylene are also presented.« less

VS4 Nanoparticles Anchored on Graphene Sheets as a High-Rate and Stable Electrode Material for Sodium Ion Batteries.

PubMed

Pang, Qiang; Zhao, Yingying; Yu, Yanhao; Bian, Xiaofei; Wang, Xudong; Wei, Yingjin; Gao, Yu; Chen, Gang

2018-02-22

The size and conductivity of the electrode materials play a significant role in the kinetics of sodium-ion batteries. Various characterizations reveal that size-controllable VS 4 nanoparticles can be successfully anchored on the surface of graphene sheets (GSs) by a simple cationic-surfactant-assisted hydrothermal method. When used as an electrode material for sodium-ion batteries, these VS 4 @GS nanocomposites show large specific capacity (349.1 mAh g -1 after 100 cycles), excellent long-term stability (84 % capacity retention after 1200 cycles), and high rate capability (188.1 mAh g -1 at 4000 mA g -1 ). A large proportion of the capacity was contributed by capacitive processes. This remarkable electrochemical performance was attributed to synergistic interactions between nanosized VS 4 particles and a highly conductive graphene network, which provided short diffusion pathways for Na + ions and large contact areas between the electrolyte and electrode, resulting in considerably improved electrochemical kinetic properties. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

Sepehr, Fatemeh; Paddison, Stephen J

2015-06-04

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

Mixed titanium, silicon, and aluminum oxide nanostructures as novel adsorbent for removal of rhodamine 6G and methylene blue as cationic dyes from aqueous solution.

PubMed

Pal, Umapada; Sandoval, Alberto; Madrid, Sergio Isaac Uribe; Corro, Grisel; Sharma, Vivek; Mohanty, Paritosh

2016-11-01

Mixed oxide nanoparticles containing Ti, Si, and Al of 8-15 nm size range were synthesized using a combined sol-gel - hydrothermal method. Effects of composition on the structure, morphology, and optical properties of the nanoparticles were studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), microRaman spectroscopy, and diffuse reflectance spectroscopy (DRS). Dye removal abilities of the nanoparticles from aqueous solutions were tested for different cationic dyes. While all the mixed oxide nanoparticles revealed high and fast adsorption of cationic dyes, the particles containing Ti and Si turned out to be the best. The adsorption kinetics and equilibrium adsorption behavior of the adsorbate - adsorbent systems could be well described by pseudo-second-order kinetics and Langmuir isotherm model, respectively. Estimated thermodynamic parameters revealed the adsorption process is spontaneous, driven mainly by the electrostatic force between the cationic dye molecules and negative charge at nanoparticle surface. Highest dye adsorption capacity (162.96 mg MB/g) of the mixed oxide nanostructures containing Ti and Si is associated to their high specific surface area, and the presence of surface Si-O(δ-) groups, in addition to the hydroxyl groups of amorphous titania. Mixed oxide nanoparticles containing 75% Ti and 25% Si seen to be the most efficient adsorbents for removing cationic dye molecules from wastewater. Copyright © 2016 Elsevier Ltd. All rights reserved.

Measurements of the streaming potential of clay soils from tropical and subtropical regions using self-made apparatus.

PubMed

Li, Zhong-Yi; Li, Jiu-Yu; Liu, Yuan; Xu, Ren-Kou

2014-09-01

The streaming potential has been wildly used in charged parallel plates, capillaries, and porous media. However, there have been few studies involving the ζ potential of clay soils based on streaming potential measurements. A laboratory apparatus was developed in this study to measure the streaming potential (ΔE) of bulk clay soils' coupling coefficient (C) and cell resistance (R) of saturated granular soil samples. Excellent linearity of ΔE versus liquid pressure (ΔP) ensured the validity of measurements. The obtained parameters of C and R can be used to calculate the ζ potential of bulk soils. The results indicated that the ζ potentials measured by streaming potential method were significantly correlated with the ζ potentials of soil colloids determined by electrophoresis (r (2) = 0.960**). Therefore, the streaming potential method can be used to study the ζ potentials of bulk clay soils. The absolute values of the ζ potentials of four soils followed the order: Ultisol from Jiangxi > Ultisol from Anhui > Oxisol from Guangdong > Oxisol from Hainan, and this was consistent with the cation exchange capacities of these soils. The type and concentration of electrolytes affected soil ζ potentials. The ζ potential became less negative with increased electrolyte concentration. The ζ potentials were more negative in monovalent than in divalent cationic electrolyte solutions because more divalent cations were distributed in the shear plane of the diffuse layer as counter-cations on the soil surfaces than monovalent cations at the same electrolyte concentration.

Role of charge screening and delocalization for lipophilic cation permeability of model and mitochondrial membranes.

PubMed

Trendeleva, Tatiana A; Sukhanova, Evgenia I; Rogov, Anton G; Zvyagilskaya, Renata A; Seveina, Inna I; Ilyasova, Tatiana M; Cherepanov, Dmitry A; Skulachev, Vladimir P

2013-09-01

The effects of the mitochondria-targeted lipophilic cation dodecyltriphenylphosphonium (C12TPP, the charge is delocalized and screened by bulky hydrophobic residues) and those of lipophilic cations decyltriethylammonium bromide and cetyltrimethylammonium bromide (C10TEA and C16TMA, the charges are localized and screened by less bulky residues) on bilayer planar phospholipid membranes and tightly-coupled mitochondria from the yeast Yarrowia lipolytica have been compared. In planar membranes, C12TPP was found to generate a diffusion potential as if it easily penetrates these membranes. In the presence of palmitate, C12TPP induced H(+) permeability like plastoquinonyl decyltriphenilphosphonium that facilitates transfer of fatty acid anions (Severin et al., PNAS, 2010, 107, 663-668). C12TPP was shown to stimulate State 4 respiration of mitochondria and caused a mitochondrial membrane depolarization with a half-maximal effect at 6μM. Besides, C12TPP profoundly potentiated the uncoupling effect of endogenous or added fatty acids. C10TEA and C16TMA inhibited State 4 respiration and decreased the membrane potential, though at much higher concentrations than C12TPP, and they did not promote the uncoupling action of fatty acids. These relationships were modeled by molecular dynamics. They can be explained by different membrane permeabilities for studied cations, which in turn are due to different availabilities of the positive charge in these cations to water dipoles. Copyright © 2012 Elsevier B.V. All rights reserved.

Electrochemical Formation of Divalent Samarium Cation and Its Characteristics in LiCl-KCl Melt.

PubMed

Bae, Sang-Eun; Jung, Tae Sub; Cho, Young-Hwan; Kim, Jong-Yun; Kwak, Kyungwon; Park, Tae-Hong

2018-06-28

The electrochemical reduction of trivalent samarium in a LiCl-KCl eutectic melt produced highly stable divalent samarium, whose electrochemical properties and electronic structure in the molten salt were investigated using cyclic voltammetry, UV-vis absorption spectroscopy, laser-induced emission spectroscopy, and density functional theory (DFT) calculations. Diffusion coefficients of Sm 2+ and Sm 3+ were electrochemically measured to be 0.92 × 10 -5 and 1.10 × 10 -5 cm 2 /s, respectively, and the standard apparent potential of the Sm 2+/3+ couple was estimated to be -0.82 V vs Ag|Ag + at 450 °C. The spectroelectrochemical study demonstrated that the redox behavior of the samarium cations obeys the Nernst equation ( E°' = -0.83 V, n = 1) and the trivalent samarium cation was successfully converted to the divalent cation having characteristic absorption bands at 380 and 530 nm with molar absorptivity values of 1470 and 810 M -1 cm -1 , respectively. Density function theory calculations for the divalent samarium complex revealed that the absorption signals originated from the 4f 6 to 4f 5 5d 1 transitions. Additionally, laser-induced emission measurements for the Sm cations in the LiCl-KCl matrix showed that the Sm 3+ ion in the LiCl-KCl melt at 450 °C emitted an orange color of fluorescence, whereas a red colored emission was observed from the Sm 2+ ion in the solidified LCl-KCl salt at room temperature.

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

Electron-impact excitation of diatomic hydride cations II: OH+ and SH+

NASA Astrophysics Data System (ADS)

Hamilton, James R.; Faure, Alexandre; Tennyson, Jonathan

2018-05-01

R-matrix calculations combined with the adiabatic-nuclei-rotation and Coulomb-Born approximations are used to compute electron-impact rotational rate coefficients for two open-shell diatomic cations of astrophysical interest: the hydoxyl and sulphanyl ions, OH+ and SH+. Hyperfine resolved rate coefficients are deduced using the infinite-order-sudden approximation. The propensity rule ΔF = Δj = ΔN = ±1 is observed, as is expected for cations with a large dipole moment. A model for OH+ excitation in the Orion Bar photon-dominated region is presented which nicely reproduces Herschel observations for an electron fraction xe = 10-4 and an OH+ column density of 3 × 1013 cm-2. Electron-impact electronic excitation cross-sections and rate coefficients for the ions are also presented.

Exchangeable cations-mediated photodegradation of polycyclic aromatic hydrocarbons (PAHs) on smectite surface under visible light.

PubMed

Jia, Hanzhong; Li, Li; Chen, Hongxia; Zhao, Yue; Li, Xiyou; Wang, Chuanyi

2015-04-28

Clay minerals saturated with different exchangeable cations are expected to play various roles in photodegradation of polycyclic aromatic hydrocarbons (PAHs) via direct and/or indirect pathways on clay surfaces. In the present study, anthracene and phenanthrene were selected as molecule probes to investigate the roles of exchangeable cations on their photodegradation under visible light irradiation. For five types of cation-modified smectite clays, the photodegradation rate of anthracene and phenanthrene follows the order: Fe(3+)>Al(3+)>Cu(2+)>Ca(2+)>K(+)>Na(+), which is consistent with the binding energy of cation-π interactions between PAHs and exchangeable cations. The result suggests that PAHs photolysis rate depends on cation-π interactions on clay surfaces. Meanwhile, the deposition of anthracene at the Na(+)-smectite and K(+)-smectite surface favors solar light absorption, resulting in enhanced direct photodecomposition of PAHs. On the other hand, smectite clays saturated with Fe(3+), Al(3+), and Cu(2+) are highly photoreactive and can act as potential catalysts giving rise to oxidative radicals such as O2(-) , which initiate the transformation of PAHs. The present work provides valuable insights into understanding the transformation and fate of PAHs in the natural soil environment and sheds light on the development of technologies for contaminated land remediation. Copyright © 2015 Elsevier B.V. All rights reserved.

Diffusion doping in quantum dots: bond strength and diffusivity.

PubMed

Saha, Avijit; Makkar, Mahima; Shetty, Amitha; Gahlot, Kushagra; A R, Pavan; Viswanatha, Ranjani

2017-02-23

Semiconducting materials uniformly doped with optical or magnetic impurities have been useful in a number of potential applications. However, clustering or phase separation during synthesis has made this job challenging. Recently the "inside out" diffusion doping was proposed to be successful in obtaining large sized quantum dots (QDs) uniformly doped with a dilute percentage of dopant atoms. Herein, we demonstrate the use of basic physical chemistry of diffusion to control the size and concentration of the dopants within the QDs for a given transition metal ion. We have studied three parameters; the bond strength of the core molecules and the diffusion coefficient of the diffusing metal ion are found to be important while the ease of cation exchange was not highly influential in the control of size and concentration of the single domain dilute magnetic semiconductor quantum dots (DMSQDs) with diverse dopant ions M 2+ (Fe 2+ , Ni 2+ , Co 2+ , Mn 2+ ). Steady state optical emission spectra reveal that the dopants are incorporated inside the semiconducting CdS and the emission can be tuned during shell growth. We have shown that this method enables control over doping percentage and the QDs show a superior ferromagnetic response at room temperature as compared to previously reported systems.

A fuel-cell reactor for the direct synthesis of hydrogen peroxide alkaline solutions from H(2) and O(2).

PubMed

Yamanaka, Ichiro; Onisawa, Takeshi; Hashimoto, Toshikazu; Murayama, Toru

2011-04-18

The effects of the type of fuel-cell reactors (undivided or divided by cation- and anion-exchange membranes), alkaline electrolytes (LiOH, NaOH, KOH), vapor-grown carbon fiber (VGCF) cathode components (additives: none, activated carbon, Valcan XC72, Black Pearls 2000, Seast-6, and Ketjen Black), and the flow rates of anolyte (0, 1.5, 12 mL h(-1)) and catholyte (0, 12 mL h(-1)) on the formation of hydrogen peroxide were studied. A divided fuel-cell system, O(2) (g)|VGCF-XC72 cathode|2 M NaOH catholyte|cation-exchange membrane (Nafion-117)|Pt/XC72-VGCF anode|2 M NaOH anolyte at 12 mL h(-1) flow|H(2) (g), was effective for the selective formation of hydrogen peroxide, with 130 mA cm(-2) , a 2 M aqueous solution of H(2)O(2)/NaOH, and a current efficiency of 95 % at atmospheric pressure and 298 K. The current and formation rate gradually decreased over a long period of time. The cause of the slow decrease in electrocatalytic performance was revealed and the decrease was stopped by a flow of catholyte. Cyclic voltammetry studies at the VGCF-XC72 electrode indicated that fast diffusion of O(2) from the gas phase to the electrode, and quick desorption of hydrogen peroxide from the electrode to the electrolyte were essential for the efficient formation of solutions of H(2)O(2)/NaOH. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of molecular exchange on water droplet size analysis as determined by diffusion NMR: The W/O/W double emulsion case.

PubMed

Vermeir, Lien; Sabatino, Paolo; Balcaen, Mathieu; Declerck, Arnout; Dewettinck, Koen; Martins, José C; Guthausen, Gisela; Van der Meeren, Paul

2016-08-01

The accuracy of the inner water droplet size determination of W/O/W emulsions upon water diffusion measurement by diffusion NMR was evaluated. The resulting droplet size data were compared to the results acquired from the diffusion measurement of a highly water soluble marker compound with low permeability in the oil layer of a W/O/W emulsion, which provide a closer representation of the actual droplet size. Differences in droplet size data obtained from water and the marker were ascribed to extra-droplet water diffusion. The diffusion data of the tetramethylammonium cation marker were measured using high-resolution pulsed field gradient NMR, whereas the water diffusion was measured using both low-resolution and high-resolution NMR. Different data analysis procedures were evaluated to correct for the effect of extra-droplet water diffusion on the accuracy of water droplet size analysis. Using the water diffusion data, the use of a low measurement temperature and diffusion delay Δ could reduce the droplet size overestimation resulting from extra-droplet water diffusion, but this undesirable effect was inevitable. Detailed analysis of the diffusion data revealed that the extra-droplet diffusion effect was due to an exchange between the inner water phase and the oil phase, rather than by exchange between the internal and external aqueous phase. A promising data analysis procedure for retrieving reliable size data consisted of the application of Einstein's diffusion law to the experimentally determined diffusion distances. This simple procedure allowed determining the inner water droplet size of W/O/W emulsions upon measurement of water diffusion by low-resolution NMR at or even above room temperature. Copyright © 2016 Elsevier Inc. All rights reserved.

Doped Y.sub.2O.sub.3 buffer layers for laminated conductors

DOEpatents

Paranthaman, Mariappan Parans [Knoxville, TN; Schoop, Urs [Westborough, MA; Goyal, Amit [Knoxville, TN; Thieme, Cornelis Leo Hans [Westborough, MA; Verebelyi, Darren T [Oxford, MA; Rupich, Martin W [Framingham, MA

2007-08-21

A laminated conductor includes a metallic substrate having a surface, a biaxially textured buffer layer supported by the surface of the metallic substrate, the biaxially textured buffer layer comprising Y.sub.2O.sub.3 and a dopant for blocking cation diffusion through the Y.sub.2O.sub.3, and a biaxially textured conductor layer supported by the biaxially textured buffer layer.

Rotational diffusion of nondipolar and charged solutes in alkyl-substituted imidazolium triflimides: effect of C2 methylation on solute rotation.

PubMed

Prabhu, Sugosh R; Dutt, G B

2014-08-07

Rotational diffusion of a nondipolar solute 2,5-dimethyl-1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DMDPP) and a charged solute rhodamine 110 (R110) has been investigated in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM][Tf2N]) and 1-butyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide ([BMMIM][Tf2N]) to understand the influence of the C2 methylation on solute rotation. The measured reorientation times of the nondipolar solute DMDPP are similar in both the ionic liquids and follow Stokes-Einstein-Debye hydrodynamic theory with slip hydrodynamics. In contrast, rotational diffusion of the charged solute R110 in [BMIM][Tf2N] obeys stick hydrodynamics due to specific interactions with the anion of the ionic liquid. Nevertheless, the intriguing result of this study is that the reorientation times of R110 in [BMMIM][Tf2N] deviate significantly from the predictions of stick hydrodynamics, especially at ambient temperatures. The solute-solvent boundary condition parameter Cobs, which is defined as the ratio of the measured reorientation time to the one calculated using the SED theory with stick boundary condition, for R110 is lower by a factor of 2 in [BMMIM][Tf2N] compared to [BMIM][Tf2N] at 298 K. Upon increasing the temperature, Cobs gradually increases and eventually matches with that obtained in [BMIM][Tf2N] at 348 K. It has been well established that methylation of the C2 position in [BMMIM][Tf2N] switches off the main hydrogen-bonding interaction between the anion and the cation, but increases the Coulombic interactions. As a consequence of the enhanced interionic interactions between the cation and anion of the ionic liquid, specific interactions between R110 and [Tf2N] diminish leading to the faster rotation of the solute. However, such an influence is not apparent in case of DMDPP as it does not experience specific interactions with either the cation or the anion of these ionic liquids.

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 the length of the alkyl chain. Although introduced mesopores alleviated the limited reagent diffusion to reactive sites due to the microporosity of the NaX zeolites, no marked improvement in the product yields was achieved with either the 1-chloroalkanes or the trialkyl phosphates test compounds, regardless of alkyl chain length. The disappointing results have been attributed to lack of substantial net increase in the numbers of zeolite nucleophilic sites accompanying mesopore introduction.

Methylene migration and coupling on a non-reducible metal oxide: The reaction of dichloromethane on stoichiometric α-Cr 2O 3(0001)

DOE PAGES

Dong, Yujung; Brooks, John D.; Chen, Tsung-Liang; ...

2014-09-17

The reaction of CH 2Cl 2 over the nearly-stoichiometric α-Cr 2O 3(0001) surface produces gas phase ethylene, methane and surface chlorine adatoms. The reaction is initiated by the decomposition of CH 2Cl 2 into surface methylene and chlorine. Photoemission indicates that surface cations are the preferred binding sites for both methylene and chlorine adatoms. Two reaction channels are observed for methylene coupling to ethylene in temperature-programmed desorption (TPD). A desorption-limited, low-temperature route is attributed to two methylenes bound at a single site. The majority of ethylene is produced by a reaction-limited process involving surface migration (diffusion) of methylene as themore » rate-limiting step. DFT calculations indicate the surface diffusion mechanism is mediated by surface oxygen anions. The source of hydrogen for methane formation is adsorbed background water. Chlorine adatoms produced by the dissociation of CH 2Cl 2 deactivate the surface by simple site-blocking of surface Cr 3+ sites. Finally, a comparison of experiment and theory shows that DFT provides a better description of the surface chemistry of the carbene intermediate than DFT+U using reported parameters for a best representation of the bulk electronic properties of α-Cr 2O 3.« less

Gas-phase reactions of carbon dioxide with atomic transition-metal and main-group cations: room-temperature kinetics and periodicities in reactivity.

PubMed

Koyanagi, Gregory K; Bohme, Diethard K

2006-02-02

The chemistry of carbon dioxide has been surveyed systematically with 46 atomic cations at room temperature using an inductively-coupled plasma/selected-ion flow tube (ICP/SIFT) tandem mass spectrometer. The atomic cations were produced at ca. 5500 K in an ICP source and allowed to cool radiatively and to thermalize by collisions with Ar and He atoms prior to reaction downstream in a flow tube in helium buffer gas at 0.35 +/- 0.01 Torr and 295 +/- 2 K. Rate coefficients and products were measured for the reactions of first-row atomic ions from K(+) to Se(+), of second-row atomic ions from Rb(+) to Te(+) (excluding Tc(+)), and of third-row atomic ions from Cs(+) to Bi(+). CO(2) was found to react in a bimolecular fashion by O atom transfer only with 9 early transition-metal cations: the group 3 cations Sc(+), Y(+), and La(+), the group 4 cations Ti(+), Zr(+), and Hf(+), the group 5 cations Nb(+) and Ta(+), and the group 6 cation W(+). Electron spin conservation was observed to control the kinetics of O atom transfer. Addition of CO(2) was observed for the remaining 37 cations. While the rate of addition was not measurable some insight was obtained into the standard free energy change, DeltaG(o), for CO(2) ligation from equilibrium constant measurements. A periodic variation in DeltaG(o) was observed for first row cations that is consistent with previous calculations of bond energies D(0)(M(+)-CO(2)). The observed trends in D(0) and DeltaG(o) are expected from the variation in electrostatic attraction between M(+) and CO(2) which follows the trend in atomic-ion size and the trend in repulsion between the orbitals of the atomic cations and the occupied orbitals of CO(2). Higher-order CO(2) cluster ions with up to four CO(2) ligands also were observed for 24 of the atomic cations while MO(2)(+) dioxide formation by sequential O atom transfer was seen only with Hf(+), Nb(+), Ta(+), and W(+).

Mixtures of the 1-ethyl-3-methylimidazolium acetate ionic liquid with different inorganic salts: insights into their interactions.

PubMed

Oliveira, Filipe S; Cabrita, Eurico J; Todorovic, Smilja; Bernardes, Carlos E S; Lopes, José N Canongia; Hodgson, Jennifer L; MacFarlane, Douglas R; Rebelo, Luís P N; Marrucho, Isabel M

2016-01-28

In this work, we explore the interactions between the ionic liquid 1-ethyl-3-methylimidazolim acetate and different inorganic salts belonging to two different cation families, those based on ammonium and others based on sodium. NMR and Raman spectroscopy are used to screen for changes in the molecular environment of the ions in the ionic liquid + inorganic salt mixtures as compared to pure ionic liquid. The ion self-diffusion coefficients are determined from NMR data, allowing the discussion of the ionicity values of the ionic liquid + inorganic salt mixtures calculated using different methods. Our data reveal that preferential interactions are established between the ionic liquid and ammonium-based salts, as opposed to sodium-based salts. Computational calculations show the formation of aggregates between the ionic liquid and the inorganic salt, which is consistent with the spectroscopic data, and indicate that the acetate anion of the ionic liquid establishes preferential interactions with the ammonium cation of the inorganic salts, leaving the imidazolium cation less engaged in the media.

Emergence of innovative properties by replacement of nitrogen atom with phosphorus atom in quaternary ammonium ionic liquids: Insights from ab initio calculations and MD simulations

NASA Astrophysics Data System (ADS)

Ghatee, Mohammad Hadi; Bahrami, Maryam

2017-06-01

We investigate to contrasting structure, dynamic and thermophysical properties of quaternary ammonium and phosphonium ionic liquids (ILs) based on triethylalkylammonium [N222n]+ and triethylalkylphosphonium [P222n]+ cations (n = 5, 8, 12) and (bis(trifluoromethylsulfonyl)imide) anion [NTf2]- by quantum chemical calculations (QCC) and molecular dynamics (MD) simulations. QCCs conform to previous studies, showing that phosphonium cation alkyl chain rotational-energy-barrier is lower than ammonium cation. These molecular nature leads to no appreciable differences in their liquid density. However, their simulated transport properties (self-diffusion, conductivity, etc) are appreciably different. In particular, viscosity of phosphoniums are much lower than ammoniums. Ammoniums make nano-scale structural domains larger than phosphoniums. Employed analysis, vector re-orientational dynamics, ion-pair lifetime and nanostructure domain are in favor of faster dynamic for phosphoniums than ammoniums. [NTf2]- anion features a long lived pairing with ammoniums than phosphoniums. Overall, phosphoniums possess higher transference number, higher conductivity, and appreciably lower viscosity favorable for higher electrochemical performances.

Formulation studies on ibuprofen sodium-cationic dextran conjugate: effect on tableting and dissolution characteristics of ibuprofen.

PubMed

Abioye, Amos Olusegun; Kola-Mustapha, Adeola

2016-01-01

The effect of electrostatic interaction between ibuprofen sodium (IbS) and cationic diethylaminoethyl dextran (Ddex), on the tableting properties and ibuprofen release from the conjugate tablet was investigated. Ibuprofen exhibits poor flow, compaction (tableting) and dissolution behavior due to its hydrophobic structure, high cohesive, adhesive and viscoelastic properties therefore it was granulated with cationic Ddex to improve its compression and dissolution characteristics. Electrostatic interaction and hydrogen bonding between IbS and Ddex was confirmed with FT-IR and DSC results showed a stepwise endothermic solid-solid structural transformation from racemic to anhydrous forms between 120 and 175 °C which melted into liquid form at 208.15 °C. The broad and diffused DSC peaks of the conjugate granules as well as the disappearance of ibuprofen melting peak provided evidence for their highly amorphous state. It was evident that Ddex improved the flowability and densification of the granules and increased the mechanical and tensile strengths of the resulting tablets as the tensile strength increased from 0.67 ± 0.0172 to 1.90 ± 0.0038 MPa with increasing Ddex concentration. Both tapping and compression processes showed that the most prominent mechanism of densification were particle slippage, rearrangement and plastic deformation while fragmentation was minimized. Ddex retarded the extent of dissolution in general, indicating potentials for controlled release formulations. Multiple release mechanisms including diffusion; anomalous transport and super case II transport were noted. It was concluded that interaction between ibuprofen sodium and Ddex produced a novel formulation with improved flowability, tableting and dissolution characteristics with potential controlled drug release characteristics dictated by Ddex concentration.

Ion Transport via Structural Relaxations in Polymerized Ionic Liquids

NASA Astrophysics Data System (ADS)

Ganesan, Venkat; Mogurampelly, Santosh

We study the mechanisms underlying ion transport in poly(1-butyl-3-vinylimidazolium-hexafluorophosphate) polymer electrolytes. We consider polymer electrolytes of varying polymerized ionic liquid to ionic liquid (polyIL:IL) ratios and use atomistic molecular dynamics (MD) simulations to probe the dynamical and structural characteristics of the electrolyte. Our results reveal that anion diffusion along polymer backbone occurs primarily viathe formation and breaking of ion-pairs involving threepolymerized cationic monomers of twodifferent polymer chains. Moreover, we observe that the ionic diffusivities exhibit a direct correlation with the structural relaxation times of the ion-pairs and hydrogen bonds (H-bonds). These results provide new insights into the mechanisms underlying ion transport in polymerized ionic liquid electrolytes.

Electrochemically influenced cation inter-diffusion and Co 3O 4 formation on La 0.6Sr 0.4CoO 3 infiltrated into SOFC cathodes

DOE PAGES

Song, Xueyan; Lee, Shiwoo; Chen, Yun; ...

2015-06-18

Nanosized LSC electrocatalyst was infiltrated into a porous scaffold cathode composed of Sm 2O 3-doped CeO 2 (SDC) and La 0.6Sr 0.4Co 0.2Fe 0.8O 3-δ (LSCF) in a commercial button solid oxide fuel cell (SOFC). To understand the stability of cathodes infiltrated with LSC, the infiltrated composite cells were subjected to both electrochemical operating and thermal aging states at 750 °C for 1500 h. Nanostructure and local chemistry evolution of La 0.6Sr 0.4CoO 3 (LSC) infiltrated cathodes upon operation and aging were investigated by transmission electron microscopy. After operation, the LSC remained a cubic perovskite, and the crystal grains exhibitmore » comparable size to as-infiltrated LSC grains. Inter-diffusion of Fe from the LSCF to a Fe-incorporated LSC layer developed on the LSCF backbone. However, only sharp interfaces were observed between LSC and SDC backbone in the as-infiltrated cathode and such interfaces remain after operation. The infiltrated LSC on the SDC backbone also retains granular particle morphology. Furthermore, newly grown Co 3O 4 nanocrystals were found in the operated cathode. After thermal aging, on the other hand, cation inter-diffusion across the interfaces of the infiltrate particles and the cathode backbones is less than that from the operated cells. Lastly, the following hypothesis is proposed: Co 3O 4 forms on LSC arising from local charge balancing between cobalt and oxygen vacancies.« less

Electron-impact excitation of diatomic hydride cations - I. HeH+, CH+, ArH+

NASA Astrophysics Data System (ADS)

Hamilton, James R.; Faure, Alexandre; Tennyson, Jonathan

2016-01-01

R-matrix calculations combined with the adiabatic nuclei approximation are used to compute electron-impact rotational excitation rates for three closed-shell diatomic cations, HeH+, CH+, ArH+. Comparisons with previous studies show that an improved treatment of threshold effects leads to significant changes in the low temperature rates; furthermore the new calculations suggest that excitation of CH+ is dominated by ΔJ = 1 transitions as is expected for cations with a large dipole moment. A model for ArH+ excitation in the Crab nebula is presented which gives results consistent with the observations for electron densities in the range 2-3 × 103 cm-3.

Reverse weathering in marine sediments and the geochemical cycle of potassium in seawater: Insights from the K isotopic composition (41K/39K) of deep-sea pore-fluids

USGS Publications Warehouse

Santiago Ramos, Danielle P.; Morgan, Leah; Lloyd, Nicholas S.; Higgins, John A.

2018-01-01

In situ Al-silicate formation, also known as “reverse weathering,” is an important sink of many of the major and minor cations in seawater (e.g. Mg, K, and Li). However, the importance of this sink in global geochemical cycles and isotopic budgets of these elements remains poorly constrained. Here, we report on the potassium isotopic composition (41">41K/39">39K) of deep-sea sediment pore-fluids from four (Integrated) Ocean Drilling Program sites (1052, U1378, U1395 and U1403) to characterize potassium isotopic fractionation associated with the formation of authigenic Al-silicate minerals in marine sediments and its role in elevating the 41">41K/39">39K of seawater relative to bulk silicate Earth. Isotopic ratios are obtained by high-resolution multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) in cold plasma conditions with a long-term external reproducibility of ca. 0.17‰. We find that, although all sites are characterized by pore-fluid K concentrations that decline with increasing depth, their K isotopic profiles vary systematically from site-to-site; at sites characterized by rapid sedimentation rates, pore-fluid profiles of 41">41K/39">39K are relatively invariant whereas at sites characterized by slow sedimentation rates, 41">41K/39">39K declines with depth by up to 1.8‰. Results from 1-D diffusion-advection-reaction models suggest that these differences may result from a complex interplay between sedimentation rate and fractionation of K isotopes during diffusion, Al-silicate authigenesis, and ion exchange. Model simulations suggest fractionation factors between 0.9980 and 1.0000 for reverse weathering reactions in deep-sea sediments. Although deep-sea sites do not constitute major sinks of K in seawater, some of the processes responsible for K isotopic fractionation at these sites (diffusion and Al-silicate authigenesis) likely play a role in determining the 41">41K/39">39K of seawater.

The relationship between the surface composition and electrical properties of corrosion films formed on carbon steel in alkaline sour medium: an XPS and EIS study.

PubMed

Galicia, Policarpo; Batina, Nikola; González, Ignacio

2006-07-27

This work studies the evolution of 1018 carbon steel surfaces during 3-15 day immersion in alkaline sour medium 0.1 M (NH4)2S and 10 ppm CN(-) as (NaCN). During this period of time, surfaces were jointly characterized by electrochemical techniques in situ (electrochemical impedance spectroscopy, EIS) and spectroscopic techniques ex situ (X-ray photoelectron spectroscopy, XPS). The results obtained by these techniques allowed for a description of electrical and chemical properties of the films of corrosion products formed at the 1018 steel surface. There is an interconversion cycle of chemical species that form films of corrosion products whose conversion reactions favor two different types of diffusions inside the films: a chemical diffusion of iron cations and a typical diffusion of atomic hydrogen. These phenomena jointly control the passivity of the interface attacked by the corrosive medium.

Ionic-to-Electronic Conductivity Crossover in CdTe-AgI-As2Te3 Glasses: An 110mAg Tracer Diffusion Study.

PubMed

Kassem, M; Alekseev, I; Bokova, M; Le Coq, D; Bychkov, E

2018-04-12

Conductivity isotherms of (CdTe) x (AgI) 0.5- x/2 (As 2 Te 3 ) 0.5- x/2 glasses (0.0 ≤ x ≤ 0.15) reveal a nonmonotonic behavior with increasing CdTe content reminiscent of mixed cation effect in oxide and chalcogenide glasses. Nevertheless, the apparent similarity appears to be partly incorrect. Using 110m Ag tracer diffusion measurements, we show that semiconducting CdTe additions produce a dual effect: (i) decreasing the Ag + ion transport by a factor of ≈200 with a simultaneous increase of the diffusion activation energy and (ii) increasing the electronic conductivity by 1.5 orders of magnitude. Consequently, the conductivity minimum at x = 0.05 reflects an ionic-to-electronic transport crossover; the silver-ion transport number decreases by 3 orders of magnitude with increasing x.

Electrostatic interactions in soft particle systems: mesoscale simulations of ionic liquids.

PubMed

Wang, Yong-Lei; Zhu, You-Liang; Lu, Zhong-Yuan; Laaksonen, Aatto

2018-05-21

Computer simulations provide a unique insight into the microscopic details, molecular interactions and dynamic behavior responsible for many distinct physicochemical properties of ionic liquids. Due to the sluggish and heterogeneous dynamics and the long-ranged nanostructured nature of ionic liquids, coarse-grained meso-scale simulations provide an indispensable complement to detailed first-principles calculations and atomistic simulations allowing studies over extended length and time scales with a modest computational cost. Here, we present extensive coarse-grained simulations on a series of ionic liquids of the 1-alkyl-3-methylimidazolium (alkyl = butyl, heptyl-, and decyl-) family with Cl, [BF4], and [PF6] counterions. Liquid densities, microstructures, translational diffusion coefficients, and re-orientational motion of these model ionic liquid systems have been systematically studied over a wide temperature range. The addition of neutral beads in cationic models leads to a transition of liquid morphologies from dispersed apolar beads in a polar framework to that characterized by bi-continuous sponge-like interpenetrating networks in liquid matrices. Translational diffusion coefficients of both cations and anions decrease upon lengthening of the neutral chains in the cationic models and by enlarging molecular sizes of the anionic groups. Similar features are observed in re-orientational motion and time scales of different cationic models within the studied temperature range. The comparison of the liquid properties of the ionic systems with their neutral counterparts indicates that the distinctive microstructures and dynamical quantities of the model ionic liquid systems are intrinsically related to Coulombic interactions. Finally, we compared the computational efficiencies of three linearly scaling O(N log N) Ewald summation methods, the particle-particle particle-mesh method, the particle-mesh Ewald summation method, and the Ewald summation method based on a non-uniform fast Fourier transform technique, to calculate electrostatic interactions. Coarse-grained simulations were performed using the GALAMOST and the GROMACS packages and hardware efficiently utilizing graphics processing units on a set of extended [1-decyl-3-methylimidazolium][BF4] ionic liquid systems of up to 131 072 ion pairs.

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

PubMed Central

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

2016-01-01

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

Anisotropic diffusion at the field scale in a 4-year multi-tracer diffusion and retention experiment - I: Insights from the experimental data

NASA Astrophysics Data System (ADS)

Gimmi, Thomas; Leupin, Olivier X.; Eikenberg, Jost; Glaus, Martin A.; Van Loon, Luc R.; Waber, H. Niklaus; Wersin, Paul; Wang, Hao A. O.; Grolimund, Daniel; Borca, Camelia N.; Dewonck, Sarah; Wittebroodt, Charles

2014-01-01

Claystones are considered worldwide as barrier materials for nuclear waste repositories. In the Mont Terri underground research laboratory (URL), a nearly 4-year diffusion and retention (DR) experiment has been performed in Opalinus Clay. It aimed at (1) obtaining data at larger space and time scales than in laboratory experiments and (2) under relevant in situ conditions with respect to pore water chemistry and mechanical stress, (3) quantifying the anisotropy of in situ diffusion, and (4) exploring possible effects of a borehole-disturbed zone. The experiment included two tracer injection intervals in a borehole perpendicular to bedding, through which traced artificial pore water (APW) was circulated, and a pressure monitoring interval. The APW was spiked with neutral tracers (HTO, HDO, H2O-18), anions (Br, I, SeO4), and cations (Na-22, Ba-133, Sr-85, Cs-137, Co-60, Eu-152, stable Cs, and stable Eu). Most tracers were added at the beginning, some were added at a later stage. The hydraulic pressure in the injection intervals was adjusted according to the measured value in the pressure monitoring interval to ensure transport by diffusion only. Concentration time-series in the APW within the borehole intervals were obtained, as well as 2D concentration distributions in the rock at the end of the experiment after overcoring and subsampling which resulted in ∼250 samples and ∼1300 analyses. As expected, HTO diffused the furthest into the rock, followed by the anions (Br, I, SeO4) and by the cationic sorbing tracers (Na-22, Ba-133, Cs, Cs-137, Co-60, Eu-152). The diffusion of SeO4 was slower than that of Br or I, approximately proportional to the ratio of their diffusion coefficients in water. Ba-133 diffused only into ∼0.1 m during the ∼4 a. Stable Cs, added at a higher concentration than Cs-137, diffused further into the rock than Cs-137, consistent with a non-linear sorption behavior. The rock properties (e.g., water contents) were rather homogeneous at the centimeter scale, with no evidence of a borehole-disturbed zone. In situ anisotropy ratios for diffusion, derived for the first time directly from field data, are larger for HTO and Na-22 (∼5) than for anions (∼3-4 for Br and I). The lower ionic strength of the pore water at this location (∼0.22 M) as compared to locations of earlier experiments in the Mont Terri URL (∼0.39 M) had no notable effect on the anion accessible pore fraction for Cl, Br, and I: the value of 0.55 is within the range of earlier data. Detailed transport simulations involving different codes will be presented in a companion paper.

Biological Effects of Short, High-Level Exposure to Gases: Sulfur Dioxide.

DTIC Science & Technology

1980-05-01

irritation and moist rales, bilaterally and anteriorly over the large bronchi. One-half of the subjects exposed to sulfur dioxide at concentrations of... burns . The pharyngeal mucosa was hyperemic but without ulceration . These men had decreased breath sounds, diffuse rales and rhonchi, with essentially...workplace have limited appli- cation in the military setting; the basis for their selection is the protection of chronically exposed workers against

A new model to study the phase transition from microstructures to nanostructures in ionic/ionic surfactants mixture.

PubMed

Sohrabi, Beheshteh; Gharibi, Hussein; Javadian, Soheila; Hashemianzadeh, Majid

2007-08-30

The phase behavior and aggregate structures of mixtures of the oppositely charged surfactants cetyltrimethyl ammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) are explored at high dilution by pulsed field gradient stimulated echo (PFG-STE) NMR. The aggregation numbers and hydrodynamic radii of vesicles and mixed micelles were determined by a combination of viscosity and self-diffusion coefficient measurements. The average size of the mixed micelles was larger than that of micelles containing uniformly charged head groups. Analysis of the variations of the self-diffusion coefficient and viscosity with changing concentration of CTAB or SDS in the cationic-rich and anionic-rich regions revealed a phase transition from vesicles to mixed micelles. Differences in the lengths of the CTAB and SDS hydrophobic chains stabilize vesicles relative to other microstructures (e.g., liquid crystalline and precipitate phase), and vesicles form spontaneously over a wide range of compositions in both cationic-rich and anionic-rich solutions. The results obtained from conductometry measurements confirmed this transition. Finally, according to the capacitor model, a new model was developed for estimating the surface potentials and electrostatic free energy (g(elec)). Then we investigated the variations of electrostatic and transfer free energy in phase transition between mixed micelle and vesicle.

Regulation of Sodium Transport in the Inner Ear

PubMed Central

Kim, Sung Huhn; Marcus, Daniel C.

2011-01-01

Na+ concentrations in endolymph must be controlled to maintain hair cell function since the transduction channels of hair cells are cation-permeable, but not K+-selective. Flooding or fluctuations of the hair cell cytosol with Na+ would be expected to lead to cellular dysfunction, hearing loss and vertigo. This review briefly describes cellular mechanisms known to be responsible for Na+homeostasis in each compartment of the inner ear, including the cochlea, saccule, semicircular canals and endolymphatic sac. The influx of Na+into endolymph of each of the organs is likely via passive diffusion, but these pathways have not yet been identified or characterized. Na+ absorption is controlled by gate -keeper channels in the apical (endolymphatic) membrane of the transporting cells. Highly Na+-selective epithelial sodium channels (ENaC) control absorption by Reissner’s membrane, saccular extramacular epithelium, semicircular canal duct epithelium and endolymphatic sac. ENaC activity is controlled by a number of signal pathways, but most notably by genomic regulation of channel numbers in the membrane via glucocorticoid signaling. Nonselective cation channels in the apical membrane of outer sulcus epithelial cells and vestibular transitional cells mediate Na+ and parasensory K+ absorption. The K+-mediated transduction current in hair cells is also accompanied by a Na+ flux since the transduction channels are nonselective cation channels. Cation absorption by all of these cells is regulated by extracellular ATP via apical nonselective cation channels (P2X receptors). The heterogeneous population of epithelial cells in the endolymphatic sac is thought to have multiple absorptive pathways for Na+ with regulatory pathways that include glucocorticoids and purinergic agonists. PMID:21620939

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

PubMed Central

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

2016-01-01

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

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

PubMed

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

2016-05-10

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

Structural, Chemical, and Dynamical Frustration: Origins of Superionic Conductivity in closo -Borate Solid Electrolytes

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

Kweon, Kyoung E.; Varley, Joel B.; Shea, Patrick

Li 2B 12H 12, Na 2B 12H 12, and their closo-borate relatives exhibit unusually high ionic conductivity, making them attractive as a new class of candidate electrolytes in solid-state Li- and Na-ion batteries. However, further optimization of these materials requires a deeper understanding of the fundamental mechanisms underlying ultrafast ion conduction. To this end, we use ab initio molecular dynamics simulations and density-functional calculations to explore the motivations for cation diffusion. We find that superionic behavior in Li 2B 12H 12 and Na 2B 12H 12 results from a combination of key structural, chemical, and dynamical factors that introduce intrinsicmore » frustration and disorder. A statistical metric is used to show that the structures exhibit a high density of accessible interstitial sites and site types, which correlates with the flatness of the energy landscape and the observed cation mobility. Furthermore, cations are found to dock to specific anion sites, leading to a competition between the geometric symmetry of the anion and the symmetry of the lattice itself, which can facilitate cation hopping. Finally, facile anion reorientations and other low-frequency thermal vibrations lead to fluctuations in the local potential that enhance cation mobility by creating a local driving force for hopping. In conclusion, we discuss the relevance of each factor for developing new ionic conductivity descriptors that can be used for discovery and optimization of closo-borate solid electrolytes, as well as superionic conductors more generally.« less

Structural, Chemical, and Dynamical Frustration: Origins of Superionic Conductivity in closo -Borate Solid Electrolytes

DOE PAGES

Kweon, Kyoung E.; Varley, Joel B.; Shea, Patrick; ...

2017-10-11

Li 2B 12H 12, Na 2B 12H 12, and their closo-borate relatives exhibit unusually high ionic conductivity, making them attractive as a new class of candidate electrolytes in solid-state Li- and Na-ion batteries. However, further optimization of these materials requires a deeper understanding of the fundamental mechanisms underlying ultrafast ion conduction. To this end, we use ab initio molecular dynamics simulations and density-functional calculations to explore the motivations for cation diffusion. We find that superionic behavior in Li 2B 12H 12 and Na 2B 12H 12 results from a combination of key structural, chemical, and dynamical factors that introduce intrinsicmore » frustration and disorder. A statistical metric is used to show that the structures exhibit a high density of accessible interstitial sites and site types, which correlates with the flatness of the energy landscape and the observed cation mobility. Furthermore, cations are found to dock to specific anion sites, leading to a competition between the geometric symmetry of the anion and the symmetry of the lattice itself, which can facilitate cation hopping. Finally, facile anion reorientations and other low-frequency thermal vibrations lead to fluctuations in the local potential that enhance cation mobility by creating a local driving force for hopping. In conclusion, we discuss the relevance of each factor for developing new ionic conductivity descriptors that can be used for discovery and optimization of closo-borate solid electrolytes, as well as superionic conductors more generally.« less

Characterizing molecular probes for diffusion measurements in the brain

PubMed Central

Kaur, Gurjinder; Hrabetova, Sabina; Guilfoyle, David N.; Nicholson, Charles; Hrabe, Jan

2008-01-01

Brain diffusion properties are at present most commonly evaluated by magnetic resonance (MR) diffusion imaging. MR cannot easily distinguish between the extracellular and intracellular signal components, but the older technique of Real-Time Iontophoresis (RTI) detects exclusively extracellular diffusion. Interpretation of the MR results would therefore benefit from auxiliary RTI measurements. This requires a molecular probe detectable by both techniques. Our aim was to specify a minimum set of requirements that such a diffusion probe should fulfill and apply it to two candidate probes: the cation tetramethylammonium (TMA+), used routinely in the RTI experiments, and the anion hexafluoroantimonate (SbF6−). Desirable characteristics of a molecular diffusion probe include predictable diffusion properties, stability, minimum interaction with cellular physiology, very slow penetration into the cells, and sufficiently strong and selective MR and RTI signals. These properties were evaluated using preparations of rat neocortical slices under normal and ischemic conditions, as well as solutions and agarose gel. While both molecules can be detected by MR and RTI, neither proved an ideal candidate. TMA+ was very stable but it penetrated into the cells and accumulated there within tens of minutes. SbF6− did not enter the cells as readily but it was not stable, particularly in ischemic tissue and at higher temperatures. Its presence also resulted in a decreased extracellular volume. These probe properties help to interpret previously published MR data on TMA+ diffusion and might play a role in other diffusion experiments obtained with them. PMID:18466980

Cation Exchange in the Presence of Oil in Porous Media

PubMed Central

2017-01-01

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

High rate, long cycle life battery electrode materials with an open framework structure

DOEpatents

Wessells, Colin; Huggins, Robert; Cui, Yi; Pasta, Mauro

2015-02-10

A battery includes a cathode, an anode, and an aqueous electrolyte disposed between the cathode and the anode and including a cation A. At least one of the cathode and the anode includes an electrode material having an open framework crystal structure into which the cation A is reversibly inserted during operation of the battery. The battery has a reference specific capacity when cycled at a reference rate, and at least 75% of the reference specific capacity is retained when the battery is cycled at 10 times the reference rate.

Enhanced desorption of cesium from collapsed interlayer regions in vermiculite by hydrothermal treatment with divalent cations.

PubMed

Yin, Xiangbiao; Wang, Xinpeng; Wu, Hao; Ohnuki, Toshihiko; Takeshita, Kenji

2017-03-15

Adsorption of cesium (Cs) on phyllosilicates has been intensively investigated because natural soils have strong ability of immobilizing Cs within clay minerals resulting in difficulty of decontamination. The objectives of present study are to clarify how Cs fixation on vermiculite is influenced by structure change caused by Cs sorption at different loading levels and how Cs desorption is affected by various replacing cations induced at different treating temperature. As a result, more than 80% of Cs was readily desorbed from vermiculite with loading amount of 2% saturated Cs (5.49×10 -3 mmolg -1 ) after four cycles of treatment of 0.01M Mg 2+ /Ca 2+ at room temperature, but less than 20% of Cs was desorbed from saturated vermiculite. These distinct desorption patterns were attributed to inhibition of Cs desorption by interlayer collapse of vermiculite, especially at high Cs loadings. In contrast, elevated temperature significantly facilitated divalent cations to efficiently desorb Cs from collapsed regions. After five cycles of treatment at 250°C with 0.01M Mg 2+ , ∼100% removal of saturated Cs was achieved. X-ray diffraction analysis results suggested that Cs desorption was completed through enhanced diffusion of Mg 2+ cations into collapsed interlayer space under hydrothermal condition resulting in subsequent interlayer decollapse and readily release of Cs + . Copyright © 2016 Elsevier B.V. All rights reserved.

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

PubMed Central

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

2016-01-01

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

Interactions of trace metals with hydrogels and filter membranes used in DET and DGT techniques.

PubMed

Garmo, Oyvind A; Davison, William; Zhang, Hao

2008-08-01

Equilibrium partitioning of trace metals between bulk solution and hydrogels/filter was studied. Under some conditions, trace metal concentrations were higher in the hydrogels or filter membranes compared to bulk solution (enrichment). In synthetic soft water, enrichment of cationic trace metals in polyacrylamide hydrogels decreased with increasing trace metal concentration. Enrichment was little affected by Ca and Mg in the concentration range typically encountered in natural freshwaters, indicating high affinity but low capacity binding of trace metals to solid structure in polyacrylamide gels. The apparent binding strength decreased in the sequence: Cu > Pb > Ni approximately to Cd approximately to Co and a low concentration of cationic Cu eliminated enrichment of weakly binding trace metal cations. The polyacrylamide gels also had an affinity for fulvic acid and/or its trace metal complexes. Enrichment of cationic Cd in agarose gel and hydrophilic polyethersulfone filter was independent of concentration (10 nM to 5 microM) but decreased with increasing Ca/ Mg concentration and ionic strength, suggesting that it is mainly due to electrostatic interactions. However, Cu and Pb were enriched even after equilibration in seawater, indicating that these metals additionally bind to sites within the agarose gel and filter. Compared to the polyacrylamide gels, agarose gel had a lower affinity for metal-fulvic complexes. Potential biases in measurements made with the diffusive equilibration in thin-films (DET) technique, identified by this work, are discussed.

Nature and kinetic analysis of carbon-carbon bond fragmentation reactions of cation radicals derived from SET-oxidation of lignin model compounds.

PubMed

Cho, Dae Won; Parthasarathi, Ramakrishnan; Pimentel, Adam S; Maestas, Gabriel D; Park, Hea Jung; Yoon, Ung Chan; Dunaway-Mariano, Debra; Gnanakaran, S; Langan, Paul; Mariano, Patrick S

2010-10-01

Features of the oxidative cleavage reactions of diastereomers of dimeric lignin model compounds, which are models of the major types of structural units found in the lignin backbone, were examined. Cation radicals of these substances were generated by using SET-sensitized photochemical and Ce(IV) and lignin peroxidase promoted oxidative processes, and the nature and kinetics of their C-C bond cleavage reactions were determined. The results show that significant differences exist between the rates of cation radical C1-C2 bond cleavage reactions of 1,2-diaryl-(β-1) and 1-aryl-2-aryloxy-(β-O-4) propan-1,3-diol structural units found in lignins. Specifically, under all conditions C1-C2 bond cleavage reactions of cation radicals of the β-1 models take place more rapidly than those of the β-O-4 counterparts. The results of DFT calculations on cation radicals of the model compounds show that the C1-C2 bond dissociation energies of the β-1 lignin model compounds are significantly lower than those of the β-O-4 models, providing clear evidence for the source of the rate differences.

Diffuse sorption modeling.

PubMed

Pivovarov, Sergey

2009-04-01

This work presents a simple solution for the diffuse double layer model, applicable to calculation of surface speciation as well as to simulation of ionic adsorption within the diffuse layer of solution in arbitrary salt media. Based on Poisson-Boltzmann equation, the Gaines-Thomas selectivity coefficient for uni-bivalent exchange on clay, K(GT)(Me(2+)/M(+))=(Q(Me)(0.5)/Q(M)){M(+)}/{Me(2+)}(0.5), (Q is the equivalent fraction of cation in the exchange capacity, and {M(+)} and {Me(2+)} are the ionic activities in solution) may be calculated as [surface charge, mueq/m(2)]/0.61. The obtained solution of the Poisson-Boltzmann equation was applied to calculation of ionic exchange on clays and to simulation of the surface charge of ferrihydrite in 0.01-6 M NaCl solutions. In addition, a new model of acid-base properties was developed. This model is based on assumption that the net proton charge is not located on the mathematical surface plane but diffusely distributed within the subsurface layer of the lattice. It is shown that the obtained solution of the Poisson-Boltzmann equation makes such calculations possible, and that this approach is more efficient than the original diffuse double layer model.

Effect of group electronegativity on electron transfer in bis(hydrazine) radical cations.

PubMed

Qin, Haimei; Zhong, Xinxin; Si, Yubing; Zhang, Weiwei; Zhao, Yi

2011-04-14

The radical cation of 4,10-ditert-butyl-5,9-diisopropyl-4,5,9,10-tetraazatetracyclo[6.2.2.2]-tetradecane (sBI4T(+)), as well as its substituted bis(hydrazine) radical cations, is chosen for the investigation of the electronegativity dependence of its intramolecular electron transfer. To do so, two parameters, reorganization energy and electronic coupling, are calculated with several ab initio approaches. It is found that the electronic couplings decrease with the increase of the group electronegativity while the reorganization energies do not show an explicit dependency. Furthermore, Marcus formula is employed to reveal those effect on the electron transfer rates. The predicted rates of electron transfer generally decrease with increasing group electronegativity, although not monotonically.

Synthesis of Cr3+-doped TiO2 nanoparticles: characterization and evaluation of their visible photocatalytic performance and stability.

PubMed

Mendiola-Alvarez, Sandra Yadira; Guzmán-Mar, Jorge Luis; Turnes-Palomino, Gemma; Maya-Alejandro, Fernando; Caballero-Quintero, Adolfo; Hernández-Ramírez, Aracely; Hinojosa-Reyes, Laura

2017-09-28

Cr 3+ -doped TiO 2 nanoparticles (Ti-Cr) were synthesized by microwave-assisted sol-gel method. The Ti-Cr catalyst was characterized by X-ray diffraction, ultraviolet-visible diffuse reflectance spectroscopy, N 2 adsorption-desorption analysis, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, photoluminescence spectroscopy, X-ray photoelectron spectroscopy (XPS) and zetametry. The anatase mesoporous Ti-Cr material exhibited a specific surface area of 54.5 m 2 /g. XPS analysis confirmed the proper substitution of Ti 4+ cations by Cr 3+ cations in the TiO 2 matrix. The particle size was of average size of 17 nm for the undoped TiO 2 but only 9.5 nm for Ti-Cr. The Cr atoms promoted the formation of hydroxyl radicals and modified the surface adsorptive properties of TiO 2 due to the increase in surface acidity of the material. The photocatalytic evaluation demonstrated that the Ti-Cr catalyst completely degraded (4-chloro-2-methylphenoxy) acetic acid under visible light irradiation, while undoped TiO 2 and P25 allowed 45.7% and 31.1%, respectively. The rate of degradation remained 52% after three cycles of catalyst reuse. The higher visible light photocatalytic activity of Ti-Cr was attributed to the beneficial effect of Cr 3+ ions on the TiO 2 surface creating defects within the TiO 2 crystal lattice, which can act as charge-trapping sites, reducing the electron-hole recombination process.

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.

Impact of dissolution and carbonate precipitation on carbon storage in basalt

NASA Astrophysics Data System (ADS)

Wells, R. K.; Xiong, W.; Tadeoye, J.; Menefee, A.; Ellis, B. R.; Skemer, P. A.; Giammar, D.

2016-12-01

The spatial evolution of silicate mineral dissolution, carbonate precipitation, and the transport of fluids influence the viability of carbon storage in basalt reservoirs. Dissolution of natural basalt and subsequent carbonate precipitation in systems with different transport processes operating were characterized using static and flow-through (5 mL/hr) experiments at 50, 100, and 150 °C, and 100 bar CO2. Intact samples and cores with milled pathways that simulate fractures were tested. Spatial and mineralogical patterns in dissolution and precipitation were analyzed using optical and electron microscopy, microCT scanning, and surface roughness data. Precipitates and fluid chemistry were analyzed using Raman spectroscopy, SEM-EDS, and ICP-MS. Analysis of the bulk solution and surface topography suggests dissolution of olivine and pyroxene grains begins within hours of the start of the experiments. In flow-through experiments, total effluent cation concentrations reach a peak concentration within a few hours then drop towards a steady state within a few days. In static experiments, the initial rate of cation release is faster than it is after several weeks. In both cases Ca2+, Mg2+, and Fe2+ are the dominant cations in solution in the initial stages of reaction. Lower concentrations of Na2+, K+, and Al3+, and the preservation of feldspar and matrix grains after several weeks of reaction indicate the slow reactivity of these minerals. As the reaction progresses, the surface roughness increases steadily with cavities developing at the sites of olivine and pyroxene grains. Post-reaction analysis of basalt samples reacted at static conditions with milled pathways reveals that both siderite and amorphous silica precipitated within diffusion-limited zones as early as 4-6 weeks. Siderite abundance varies with distance along the pathway with the highest concentration of carbonates 1-2 cm below the fracture opening. Siderite precipitates are large enough to fill fracture opening 100 μm wide within 4-6 weeks.

Studies on the crystalline lens. XXI. Bidirectional carrier-mediated transport of lithium

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

Kinsey, V.E.; McLean, I.W.

1974-10-01

Movement of lithium both into and out of cultured rabbit lenses occurs by processes that obey Michaelis-Menten kinetics as well as by a nonsaturable process. The parameters describing the kinetics of transport are evaluated on the basis of a modified version of a pump-leak hypothesis that was shown previously to account for the fluxes of other alkali metal cations. Potassium is a potent competitive inhibitor of the carrier-mediated transport of lithium into the lens. Lithium weakly inhibits the influx of potassium by a noncompetitive process. The observation that lithium is a weak inhibitor of potassium transport (Ki = 70 mM)more » while having a moderate affinity for its carrier (Km = 4.0 mM) suggests that more than one site may be responsible for the transport of potassium and lithium into the lens. Active transport of lithium out of the lens does not appear to involve the sodium pump, since the rate of sodium efflux is unaffected by lithium. Both influx and efflux of lithium are inhibited by ouabain (10/sup -5/ M) but not by amiloride (10/sup -4/ M) or oxytocin (20 milliunits per milliliter). Lithium displaces proportionate amounts of sodium and potassium from intracellular fluid when lenses are cultured in the presence of this cation. The nonsaturable exchange of lithium is independent of observed differences in electric potential, indicating that lithium does not permeate the lenticular membranes by simple diffusion of lithium ions, but rather as a complex with either a free anion or a carrier within the membrane. The affinity of lithium for the carrier is essentially equal to that of cesium and much lower than that for rubidium, whereas the kd of both lithium and rubidium is much higher than that for cesium. These differences indicate that a common pathway cannot be responsible for the discrimination between cations by both the pump and the leak.« less

Anomalous frequency-dependent ionic conductivity of lesion-laden human-brain tissue

NASA Astrophysics Data System (ADS)

Emin, David; Akhtari, Massoud; Fallah, Aria; Vinters, Harry V.; Mathern, Gary W.

2017-10-01

We study the effect of lesions on our four-electrode measurements of the ionic conductivity of (˜1 cm3) samples of human brain excised from patients undergoing pediatric epilepsy surgery. For most (˜94%) samples, the low-frequency ionic conductivity rises upon increasing the applied frequency. We attributed this behavior to the long-range (˜0.4 mm) diffusion of solvated sodium cations before encountering intrinsic impenetrable blockages such as cell membranes, blood vessels, and cell walls. By contrast, the low-frequency ionic conductivity of some (˜6%) brain-tissue samples falls with increasing applied frequency. We attribute this unusual frequency-dependence to the electric-field induced liberation of sodium cations from traps introduced by the unusually severe pathology observed in samples from these patients. Thus, the anomalous frequency-dependence of the ionic conductivity indicates trap-producing brain lesions.

2D nanoporous membrane for cation removal from water: Effects of ionic valence, membrane hydrophobicity, and pore size

NASA Astrophysics Data System (ADS)

Köhler, Mateus Henrique; Bordin, José Rafael; Barbosa, Marcia C.

2018-06-01

Using molecular dynamic simulations, we show that single-layers of molybdenum disulfide (MoS2) and graphene can effectively reject ions and allow high water permeability. Solutions of water and three cations with different valencies (Na+, Zn2+, and Fe3+) were investigated in the presence of the two types of membranes, and the results indicate a high dependence of the ion rejection on the cation charge. The associative characteristic of ferric chloride leads to a high rate of ion rejection by both nanopores, while the monovalent sodium chloride induces lower rejection rates. Particularly, MoS2 shows 100% of Fe3+ rejection for all pore sizes and applied pressures. On the other hand, the water permeation does not vary with the cation valence, having dependence only with the nanopore geometric and chemical characteristics. This study helps us to understand the fluid transport through a nanoporous membrane, essential for the development of new technologies for the removal of pollutants from water.

2D nanoporous membrane for cation removal from water: Effects of ionic valence, membrane hydrophobicity, and pore size.

PubMed

Köhler, Mateus Henrique; Bordin, José Rafael; Barbosa, Marcia C

2018-06-14

Using molecular dynamic simulations, we show that single-layers of molybdenum disulfide (MoS 2 ) and graphene can effectively reject ions and allow high water permeability. Solutions of water and three cations with different valencies (Na + , Zn 2+ , and Fe 3+ ) were investigated in the presence of the two types of membranes, and the results indicate a high dependence of the ion rejection on the cation charge. The associative characteristic of ferric chloride leads to a high rate of ion rejection by both nanopores, while the monovalent sodium chloride induces lower rejection rates. Particularly, MoS 2 shows 100% of Fe 3+ rejection for all pore sizes and applied pressures. On the other hand, the water permeation does not vary with the cation valence, having dependence only with the nanopore geometric and chemical characteristics. This study helps us to understand the fluid transport through a nanoporous membrane, essential for the development of new technologies for the removal of pollutants from water.

The cation-controlled and hydrogen bond-mediated shear-thickening behaviour of a tree-fern isolated polysaccharide.

PubMed

Wee, May S M; Matia-Merino, Lara; Goh, Kelvin K T

2015-10-05

The shear-thickening rheological behaviour (between 5 and 20s(-1)) of a 5% (w/w) viscoelastic gum extracted from the fronds of the native New Zealand black tree fern or mamaku in Māori was further explored by manipulating the salt content. The freeze-dried mamaku gum contained a high mineral content and sugars which upon removal via dialysis, resulted in the loss of shear thickening. However, this loss was reversible by the addition of salts to the dialysed dispersion. The mechanism of shear-thickening behaviour was therefore hypothesised to be due to shear-induced transition of intra- to intermolecular hydrogen bonding, promoted by the screening effect of cations. Mono-, di- and trivalent salts, i.e. Na(+), K(+), N(CH3)4(+), Ca(2+), Mg(2+), Al(3+) and La(3+) at concentrations between 0.001 and 1.0M were tested to support the hypothesis as well as to demonstrate the sensitivity of the biopolymer to cation valency and concentrations. The cation valency and concentration were crucial factors in determining: (i) zero-shear viscosity, (ii) critical shear rate, γ˙c (or shear rate at the onset of shear-thickening) and (iii) the extent of shear-thickening of the solution. For mono- and divalent cations these parameters were similar at equivalent ionic strengths and fairly independent of the cation type. Trivalent cations (La(3+)) however caused precipitation of the gum in the concentration range of 0.005-0.05 M but clear dispersions were obtained above 0.05 M. Copyright © 2015 Elsevier Ltd. All rights reserved.

γ-Fe₂O₃ Nanocrystalline Microspheres with Hybrid Behavior of Battery-Supercapacitor for Superior Lithium Storage.

PubMed

Tian, Lei-Lei; Zhang, Ming-Jian; Wu, Chao; Wei, Yi; Zheng, Jia-Xin; Lin, Ling-Piao; Lu, Jun; Amine, Khalil; Zhuang, Quan-Chao; Pan, Feng

2015-12-02

Maghemite (γ-Fe2O3) nanocrystalline microspheres (MNMs) self-assembled with 52 nm nanocrystals bridged with FeOOH around grain boundaries were formed by solvothermal reaction and thermal oxidation. The unique architecture endows the MNMs with the lithium storage behavior of a hybrid battery-supercapacitor electrode: initial charge capacity of 1060 mAh g(-1) at the 100 mA g(-1) rate, stable cyclic capacity of 1077.9 mAh g(-1) at the same rate after 140 cycles, and rate capability of 538.8 mAh g(-1) at 2400 mA g(-1). This outstanding performance was attributed to the nanocrystal superiority, which shortens the Li(+) diffusion paths. The mechanism of this hybrid anode material was investigated with experimental measurements and structural analysis. The results indicate that at the first discharge, the MNM nanocrystal microsphere, whose structure can buffer the volume change that occurs during lithiation/delithiation, goes through four stages: Li(+) insertion in cation vacancies, spinel-to-rocksalt transformation, Li(+) intercalation of Li(1.75+x)Fe2O3 nanocrystals, and interfacial Li storage around nanocrystal boundaries. Only the latter two stages were reversible at and after the second charging/discharging cycle, exhibiting the hybrid behavior of a battery-supercapacitor with superior lithium storage.

Effect of Alkali Metal Cations on Slow Inactivation of Cardiac Na+ Channels

PubMed Central

Townsend, Claire; Horn, Richard

1997-01-01

Human heart Na+ channels were expressed transiently in both mammalian cells and Xenopus oocytes, and Na+ currents measured using 150 mM intracellular Na+. The kinetics of decaying outward Na+ current in response to 1-s depolarizations in the F1485Q mutant depends on the predominant cation in the extracellular solution, suggesting an effect on slow inactivation. The decay rate is lower for the alkali metal cations Li+, Na+, K+, Rb+, and Cs+ than for the organic cations Tris, tetramethylammonium, N-methylglucamine, and choline. In whole cell recordings, raising [Na+]o from 10 to 150 mM increases the rate of recovery from slow inactivation at −140 mV, decreases the rate of slow inactivation at relatively depolarized voltages, and shifts steady-state slow inactivation in a depolarized direction. Single channel recordings of F1485Q show a decrease in the number of blank (i.e., null) records when [Na+]o is increased. Significant clustering of blank records when depolarizing at a frequency of 0.5 Hz suggests that periods of inactivity represent the sojourn of a channel in a slow-inactivated state. Examination of the single channel kinetics at +60 mV during 90-ms depolarizations shows that neither open time, closed time, nor first latency is significantly affected by [Na+]o. However raising [Na+]o decreases the duration of the last closed interval terminated by the end of the depolarization, leading to an increased number of openings at the depolarized voltage. Analysis of single channel data indicates that at a depolarized voltage a single rate constant for entry into a slow-inactivated state is reduced in high [Na+]o, suggesting that the binding of an alkali metal cation, perhaps in the ion-conducting pore, inhibits the closing of the slow inactivation gate. PMID:9234168

The effects of charge, polymerization, and cluster size on the diffusivity of dissolved Si species in pore water

NASA Astrophysics Data System (ADS)

Yokoyama, Tadashi; Sakuma, Hiroshi

2018-03-01

Silicon (Si) is the most abundant cation in crustal rocks. The charge and degree of polymerization of dissolved Si significantly change depending on solution pH and Si concentration. We used molecular dynamics (MD) simulations to predict the self-diffusion coefficients of dissolved Si, DSi, for 15 monomeric and polymeric species at ambient temperature. The results showed that DSi decreased with increasing negative charge and increasing degree of polymerization. The relationship between DSi and charge (Z) can be expressed by DSi/10-6 = 2.0 + 9.8e0.47Z, and that between DSi and number of polymerization (NSi) by DSi/10-6 = 9.7/NSi0.56. The results also revealed that multiple Si molecules assembled into a cluster and D decreased as the cluster size increased. Experiments to evaluate the diffusivity of Si in pore water revealed that the diffusion coefficient decreased with increasing Si concentration, a result consistent with the MD simulations. Simulation results can now be used to quantitatively assess water-rock interactions and water-concrete reactions over a wide range of environmentally relevant conditions.

Proposed quality control guidelines for antimicrobial susceptibility tests using tilmicosin.

PubMed Central

Shryock, T R; White, D W; Werner, C S; Staples, J M

1995-01-01

Quality control guidelines for tilmicosin, a novel veterinary-use-only macrolide, were developed in a multi-laboratory study according to established National Committee for Clinical Laboratory Standards (NCCLS) procedures (M23-T2). Tilmicosin was incorporated into Sensititre plates for broth microdilution endpoint testing and into two lots of 15-micrograms disks for Kirby-Bauer agar disk diffusion testing. One common lot and five unique lots of Mueller-Hinton media were used. (Broth was cation adjusted, and agar was supplemented with 5% defibrinated sheep blood.) Bacteria used for reference strains included Pasteurella haemolytica 128K, Pasteurella multocida ATCC 43137, and Staphylococcus aureus ATCC 29213 (microdilution) and ATCC 25923 (disk). Replicate tests were conducted. Disk diffusion and broth microdilution quality control ranges are proposed. PMID:7714188

Phosphonium-Organophosphate Ionic Liquids as Lubricant Additives: Effects of Cation Structure on Physicochemical and Tribological Characteristics

DOE PAGES

Barnhill, William C.; Qu, Jun; Luo, Huimin; ...

2014-11-17

In our previous work we suggest great potential for a phosphonium-organophosphate ionic liquid (IL) as an antiwear lubricant additive. In this study, a set of five ILs were carefully designed and synthesized, with identical organophosphate anions but dissimilar phosphonium cations, to allow systematic investigation of the effects of cation alkyl chain length and symmetry on physicochemical and tribological properties. Symmetric cations with shorter alkyl chains seem to increase the density and thermal stability due to closer packing. On the other hand, either higher cation symmetry or longer alkyl moieties induce a higher viscosity, though the viscosity index is dependent moremore » on molecular mass than on symmetry. While a larger cation size generally increases an IL’s solubility in nonpolar hydrocarbon oils, six-carbon seems to be the critical minimum alkyl chain length for high oil miscibility. Both the two ILs, that are mutually oil miscible, have demonstrated promising lubricating performance at 1.04% treat rate, though the symmetric-cation IL moderately outperformed the asymmetric-cation IL. Moreover, characterizations on the tribofilm formed by the best-performing symmetric-cation IL revealed the film thickness, nanostructure, and chemical composition. Our results provide fundamental insights for future molecular design in developing oil-soluble ILs as lubricant additives.« less

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

NASA Astrophysics Data System (ADS)

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

2017-07-01

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

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

Barnhill, William C.; Qu, Jun; Luo, Huimin

In our previous work we suggest great potential for a phosphonium-organophosphate ionic liquid (IL) as an antiwear lubricant additive. In this study, a set of five ILs were carefully designed and synthesized, with identical organophosphate anions but dissimilar phosphonium cations, to allow systematic investigation of the effects of cation alkyl chain length and symmetry on physicochemical and tribological properties. Symmetric cations with shorter alkyl chains seem to increase the density and thermal stability due to closer packing. On the other hand, either higher cation symmetry or longer alkyl moieties induce a higher viscosity, though the viscosity index is dependent moremore » on molecular mass than on symmetry. While a larger cation size generally increases an IL’s solubility in nonpolar hydrocarbon oils, six-carbon seems to be the critical minimum alkyl chain length for high oil miscibility. Both the two ILs, that are mutually oil miscible, have demonstrated promising lubricating performance at 1.04% treat rate, though the symmetric-cation IL moderately outperformed the asymmetric-cation IL. Moreover, characterizations on the tribofilm formed by the best-performing symmetric-cation IL revealed the film thickness, nanostructure, and chemical composition. Our results provide fundamental insights for future molecular design in developing oil-soluble ILs as lubricant additives.« less

Facile synthesis of surface-functionalized magnetic nanocomposites for effectively selective adsorption of cationic dyes

NASA Astrophysics Data System (ADS)

Hua, Yani; Xiao, Juan; Zhang, Qinqin; Cui, Chang; Wang, Chuan

2018-04-01

A new magnetic nano-adsorbent, polycatechol modified Fe3O4 magnetic nanoparticles (Fe3O4/PCC MNPs) were prepared by a facile chemical coprecipitation method using iron salts and catechol solution as precursors. Fe3O4/PCC MNPs owned negatively charged surface with oxygen-containing groups and showed a strong adsorption capacity and fast adsorption rates for the removal of cationic dyes in water. The adsorption capacity of methylene blue (MB), cationic turquoise blue GB (GB), malachite green (MG), crystal violet (CV) and cationic pink FG (FG) were 60.06 mg g- 1, 70.97 mg g- 1, 66.84 mg g- 1, 66.01 mg g- 1 and 50.27 mg g- 1, respectively. The adsorption mechanism was proposed by the analyses of the adsorption isotherms and adsorption kinetics of cationic dyes on Fe3O4/PCC MNPs. Moreover, the cationic dyes adsorbed on the MNPs as a function of contact time, pH value, temperature, coexisting cationic ions and ion strength were also investigated. These results suggested that the Fe3O4/PCC MNPs is promising to be used as a magnetic adsorbent for selective adsorption of cationic dyes in wastewater treatment.

Modeling the Time-dependent Changes in Electrical Conductivity of Basaltic Melts With Redox State

NASA Astrophysics Data System (ADS)

Pommier, A.; Gaillard, F.; Pichavant, M.

2008-12-01

The electrical conductivity σ is an efficient probe of mass transfer processes within silicate melts and magmas. Little attention has been given to the influence of redox state (fO2) on the melts conductivity. We present an experimental setup allowing electrical conductivity measurements for basaltic melts under variable fO2. We demonstrate a significant dependence of σ with fO2, allowing to characterize in situ the mechanisms and kinetics of redox changes in the melt. Experiments were conducted on basalts from Pu'u 'O'o, Hawaii, and Mt.Vesuvius, Italy. Measurements were performed cylindrical glass samples (OD: 6mm, ID: 1mm, L: 8mm) using an impedance spectrometer. Experiments were conducted in a 1atm vertical furnace, from 1200°C to 1400°C. Variable gas atmosphere (air, CO2 or CO-CO2 gas mixtures) were used, imposing ΔNNO from -1 to +7. Electrical conductivities were determined for the two melts at constant fO2, different T (constant fO2) and constant T, different fO2 (variable fO2) obtained by changing the gas composition. Isothermal reduction and oxidation cycles were performed. Glasses quenched from different T and fO2 conditions were analyzed by electron microprobe, the FeO concentration was determined by wet chemistry. In constant fO2 experiments, a small but detectable effect of fO2 on σ is evidenced. At 1300°C, the difference in the Kilauea sample conductivity between reduced (ΔNNO=-1) and oxidized (ΔNNO=+7) fO2 is <1(ohm.m)-1, the sample being more conductive when reduced. The temperature dependence of σ was fitted using Arrhenian equations, the activation energy Ea being 100kJ/mol. Sodium was identified as the main charge carrier in the melts. The fO2-effect on σ can thus be attributed to the influence of the Fe2+/Fe3+ ratio on sodium mobility. The fO2-dependence of σ was included in the model of Pommier et al.(2008), allowing the conductivity of natural melts to be calculated as a function of T, P, H2O, and fO2. Variable fO2 experiments confirmed the increase in σ when reducing the melt. At 1200°C, for both reduction-oxidation cycles, a stable value of σ following a change in fO2 is reached in 15hours, while 2hours are needed at 1400°C. The real-time changes in σ of basaltic melts following fO2 step changes were monitored. The time-dependent changes in σ are interpreted in terms of kinetics processes due to redox reequilibration between melt and gas. The evolution of σ with time can be fitted using a diffusion-limited process for reduction in CO-CO2 gas mixtures and oxidation in air. However, a reaction at the gas-melt interface probably rate limits oxidation in CO2. Reduction and oxidation rates are similar and increase with T. Oxidation-reduction rates calculated from the analysis of the conductivity evolution with time range from 10-9 to 10-8m2/s for the T range 1200-1400°C. These reaction rates are in agreement with typical alkali diffusion coefficients in basaltic melts. However, the high value of Ea (230kJ/mol) calculated from the T dependence of the oxidation-reduction rates agrees with the Ea for alkali-Earth elements. Furthermore, microprobe analyses document the existence of alkali-Earth cation fluxes during oxidations and reductions. Such cation migration probably occurs to charge-balance electron fluxes in the melt, in agreement with the study of Cooper et al. (1996). Our results suggest that the migration of alkali and alkali-Earth elements rate-limits the redox state changes in basaltic melts, and that redox mechanisms are not restricted to oxygen chemical diffusion. A discussion of chemical vs tracer oxygen diffusion studies is proposed.

Kafirin adsorption on ion-exchange resins: isotherm and kinetic studies.

PubMed

Kumar, Prashant; Lau, Pei Wen; Kale, Sandeep; Johnson, Stuart; Pareek, Vishnu; Utikar, Ranjeet; Lali, Arvind

2014-08-22

Kafirin is a natural, hydrophobic and celiac safe prolamin protein obtained from sorghum seeds. Today kafirin is found to be useful in designing delayed delivery systems and coatings of pharmaceuticals and nutraceuticals where its purity is important and this can be obtained by adsorptive chromatography. This study is the first scientific insight into the isotherm and kinetic studies of kafirin adsorption on anion- and cation-exchange resins for practical applications in preparative scale chromatography. Adsorption isotherms of kafirin were determined for five anion- and two cation-exchange resins in batch systems. Isotherm parameters such as maximum binding capacity and dissociation constant were determined from Langmuir isotherm, and adsorptive capacity and affinity constant from Freundlich isotherm. Langmuir isotherm was found to fit the adsorption equilibrium data well. Batch uptake kinetics for kafirin adsorption on these resins was also carried out and critical parameters including the diffusion coefficient, film mass transfer coefficient, and Biot number for film-pore diffusion model were calculated. Both the isotherm and the kinetic parameters were considered for selection of appropriate resin for kafirin purification. UNOsphere Q (78.26 mg/ml) and Toyopearl SP-650M (57.4 mg/ml) were found to offer better kafirin binding capacities and interaction strength with excellent uptake kinetics under moderate operating conditions. With these adsorbents, film diffusion resistance was found to be major governing factor for adsorption (Bi<10 and δ<1). Based on designer objective function, UNOsphere Q was found be best adsorbent for binding of kafirin. The data presented is valuable for designing large scale preparative adsorptive chromatographic kafirin purification systems. Copyright © 2014 Elsevier B.V. All rights reserved.

Effect of Ionic Strength and Surface Charge Density on the Kinetics of Cellulose Nanocrystal Thin Film Swelling.

PubMed

Reid, Michael S; Kedzior, Stephanie A; Villalobos, Marco; Cranston, Emily D

2017-08-01

This work explores cellulose nanocrystal (CNC) thin films (<50 nm) and particle-particle interactions by investigating film swelling in aqueous solutions with varying ionic strength (1-100 mM). CNC film hydration was monitored in situ via surface plasmon resonance, and the kinetics of liquid uptake were quantified. The contribution of electrostatic double-layer forces to film swelling was elucidated by using CNCs with different surface charges (anionic sulfate half ester groups, high and low surface charge density, and cationic trimethylammonium groups). Total water uptake in the thin films was found to be independent of ionic strength and surface chemistry, suggesting that in the aggregated state van der Waals forces dominate over double-layer forces to hold the films together. However, the rate of swelling varied significantly. The water uptake followed Fickian behavior, and the measured diffusion constants decreased with the ionic strength gradient between the film and the solution. This work highlights that nanoparticle interactions and dispersion are highly dependent on the state of particle aggregation and that the rate of water uptake in aggregates and thin films can be tailored based on surface chemistry and solution ionic strength.

Effect of cation type and concentration of nitrates on neurological disorders during experimental cerebral ischemia.

PubMed

Kuzenkov, V S; Krushinskii, A L; Reutov, V P

2013-10-01

Experiments were performed on the model of ischemic stroke due to bilateral occlusion of the carotid arteries. Nitrates had various effects on the dynamics of neurological disorders and mortality rate of Wistar rats, which depended on the cation type and concentration.

Evaluation of the antibacterial activity of a cationic polymer in aqueous solution with a convenient electrochemical method.

PubMed

Wang, Yihong; Guo, Qing; Wang, Huafu; Qian, Kun; Tian, Liang; Yao, Chen; Song, Wei; Shu, Weixia; Chen, Ping; Qi, Jinxu

2017-02-01

Quaternized chitosan is a cationic biopolymer with good antibacterial activity, biocompatibility, and biodegradability, and it has been widely applied in many fields. We have developed a convenient method to evaluate the antibacterial activity of hydroxypropyltrimethylammonium chloride chitosan (HACC) with a nonionic surfactant poloxamer in aqueous solution by monitoring the change of the oxidation peak current in cyclic voltammetry. Increasing values of the oxidation peak current were positively correlated with the antibacterial activity of HACC-poloxamer solutions. Optical microscope images, the zeta potential, and fluorescence spectroscopy showed that the aggregation state of HACC-poloxamer was related to the ratio of the two polymers and also to the antibacterial activity and oxidation peak current. At an HACC-to-poloxamer ratio of 1:0.75, the maximum surface charge density and the smooth edge of HACC-poloxamer aggregates can accelerate diffusion in aqueous solution. It is expected that this convenient method can be applied for a quick evaluation of the antibacterial activity of cationic biopolymers in aqueous solution. Graphical Abstract The cyclic voltammograms of MB in HACC/poloxamer solution, and the antibacterial efficiency against S. aureus after incubated with HACC (a) and 1/0.75 of HACC/poloxamer (b).

The structure and intermolecular forces of DNA condensates.

PubMed

Yoo, Jejoong; Aksimentiev, Aleksei

2016-03-18

Spontaneous assembly of DNA molecules into compact structures is ubiquitous in biological systems. Experiment has shown that polycations can turn electrostatic self-repulsion of DNA into attraction, yet the physical mechanism of DNA condensation has remained elusive. Here, we report the results of atomistic molecular dynamics simulations that elucidated the microscopic structure of dense DNA assemblies and the physics of interactions that makes such assemblies possible. Reproducing the setup of the DNA condensation experiments, we measured the internal pressure of DNA arrays as a function of the DNA-DNA distance, showing a quantitative agreement between the results of our simulations and the experimental data. Analysis of the MD trajectories determined the DNA-DNA force in a DNA condensate to be pairwise, the DNA condensation to be driven by electrostatics of polycations and not hydration, and the concentration of bridging cations, not adsorbed cations, to determine the magnitude and the sign of the DNA-DNA force. Finally, our simulations quantitatively characterized the orientational correlations of DNA in DNA arrays as well as diffusive motion of DNA and cations. © The Author(s) 2016. Published by Oxford University Press on behalf of Nucleic Acids Research.

The reactive element effect of ceria particle dispersion on alumina growth: A model based on microstructural observations

PubMed Central

Wang, X.; Peng, X.; Tan, X.; Wang, F.

2016-01-01

The oxidation kinetics of alumina-forming metals can be affected by adding a small amount of a reactive (normally rare earth) element oxide (RExOy) and the segregation of the reactive element (RE) ions to the growing alumina grain boundaries (GBs) has been considered as a responsible reason. However, this interpretation remains a controversial issue as to how RE ions are produced by RExOy which is thermodynamically and chemically stable in metals. The question is answered by a model that is based on transmission electron microscopy (TEM) investigation of a CeO2-dispersed nickel aluminide oxidized in air at 1100 °C. The CeO2 dispersion is incorporated into the alumina scale by the inward growth of inner α-Al2O3, where it partially dissolves producing tetravalent Ce cations which then transform to trivalent cations by trapping electrons. The trivalent cations segregate to the α-Al2O3 GBs and diffuse outward along first the GBs and later the twin boundaries (TBs) in the outer γ-Al2O3 layer, being precipitated as Ce2O3 particles near surface. PMID:27406938

Mn-euvering manganese: the role of transporter gene family members in manganese uptake and mobilization in plants

PubMed Central

Socha, Amanda L.; Guerinot, Mary Lou

2014-01-01

Manganese (Mn), an essential trace element, is important for plant health. In plants, Mn serves as a cofactor in essential processes such as photosynthesis, lipid biosynthesis and oxidative stress. Mn deficient plants exhibit decreased growth and yield and are more susceptible to pathogens and damage at freezing temperatures. Mn deficiency is most prominent on alkaline soils with approximately one third of the world's soils being too alkaline for optimal crop production. Despite the importance of Mn in plant development, relatively little is known about how it traffics between plant tissues and into and out of organelles. Several gene transporter families have been implicated in Mn transport in plants. These transporter families include NRAMP (natural resistance associated macrophage protein), YSL (yellow stripe-like), ZIP (zinc regulated transporter/iron-regulated transporter [ZRT/IRT1]-related protein), CAX (cation exchanger), CCX (calcium cation exchangers), CDF/MTP (cation diffusion facilitator/metal tolerance protein), P-type ATPases and VIT (vacuolar iron transporter). A combination of techniques including mutant analysis and Synchrotron X-ray Fluorescence Spectroscopy can assist in identifying essential transporters of Mn. Such knowledge would vastly improve our understanding of plant Mn homeostasis. PMID:24744764

Basolateral choline transport in isolated rabbit renal proximal tubules.

PubMed

Dantzler, W H; Evans, K K; Wright, S H

1998-11-01

Choline can undergo both net secretion and net reabsorption by renal proximal tubules, but at physiological plasma levels net reabsorption occurs. During this process, choline enters the cells at the luminal side down an electrochemical gradient via a specific transporter with a high affinity for choline. It appeared likely that choline was then transported out of the cells against an electrochemical gradient at the basolateral membrane by countertransport for another organic cation. This possibility was examined by studying net transepithelial reabsorption and basolateral uptake and efflux of [14C]choline in isolated S2 segments of rabbit renal proximal tubules. Basolateral uptake, which was inhibited by other organic cations such as tetraethylammonium (TEA), appeared to occur by the standard organic cation transport pathway. However, the addition of TEA to the bathing medium not only failed to trans-stimulate net transepithelial reabsorption and basolateral efflux of [14C]choline but it actually inhibited transepithelial reabsorption by @60%. The results do not support the presence of a countertransport step for choline against an electrochemical gradient at the basolateral membrane. Instead, they suggest that choline crosses this membrane by some form of carrier-mediated diffusion even during the reabsorptive process.

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

PubMed

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

1982-06-17

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

Peach gum for efficient removal of methylene blue and methyl violet dyes from aqueous solution.

PubMed

Zhou, Li; Huang, Jiachang; He, Benzhao; Zhang, Faai; Li, Huabin

2014-01-30

This study investigated the potential use of natural peach gum (PG) as alternative adsorbent for the removal of dyes from aqueous solutions. The PG showed high adsorption capacities and selectivity for cationic dyes (e.g., methylene blue (MB) and methyl violet (MV)) in the pH range 6-10. 98% of MB and MV could be adsorbed within 5 min, and both of the adsorptions reached equilibrium within 30 min. The dye uptake process followed the pseudo-second-order kinetic model. The intraparticle diffusion was not the sole rate controlling step. Equilibrium adsorption isotherm data indicated a good fit to the Langmuir isotherm model. Regeneration study revealed that PG could be well regenerated in acid solution. The recovered PG still exhibited high adsorption capacity even after five cycles of desorption-adsorption. On the basis of its excellent adsorption performance and facile availability, PG can be employed as an efficient low cost adsorbent for environmental cleanup. Copyright © 2013 Elsevier Ltd. All rights reserved.

Molecular understanding of polyelectrolyte binders that actively regulate ion transport in sulfur cathodes

DOE PAGES

Li, Longjun; Pascal, Tod A.; Connell, Justin G.; ...

2017-12-22

Polymer binders in battery electrodes may be either active or passive. This distinction depends on whether the polymer influences charge or mass transport in the electrode. Though it is desirable to understand how to tailor the macromolecular design of a polymer to play a passive or active role, design rules are still lacking, as is a framework to assess the divergence in such behaviors. We reveal the molecular-level underpinnings that distinguish an active polyelectrolyte binder designed for lithium-sulfur batteries from a passive alternative. The binder, a cationic polyelectrolyte, is shown to both facilitate lithium-ion transport through its reconfigurable network ofmore » mobile anions and restrict polysulfide diffusion from mesoporous carbon hosts by anion metathesis, which we show is selective for higher oligomers. These attributes then allow cells to be operated for > 100 cycles with excellent rate capability using cathodes with areal sulfur loadings up to 8.1 mg cm -2 .« less

Infrared spectroscopic characterization of dehydration and accompanying phase transition behaviors in NAT-topology zeolites

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

Wang, Hsiu-Wen; Bishop, David

2012-01-01

Relative humidity (PH2O, partial pressure of water)-dependent dehydration and accompanying phase transitions in NAT-topology zeolites (natrolite, scolecite, and mesolite) were studied under controlled temperature and known PH2O conditions by in situ diffuse-reflectance infrared Fourier transform spectroscopy and parallel X-ray powder diffraction. Dehydration was characterized by the disappearance of internal H2O vibrational modes. The loss of H2O molecules caused a sequence of structural transitions in which the host framework transformation path was coupled primarily via the thermal motion of guest Na?/Ca2? cations and H2O molecules. The observation of different interactions of H2O molecules and Na?/Ca2? cations with host aluminosilicate frameworks undermore » highand low-PH2O conditions indicated the development of different local strain fields, arising from cation H2O interactions in NAT-type channels. These strain fields influence the Si O/Al O bond strength and tilting angles within and between tetrahedra as the dehydration temperature is approached. The newly observed infrared bands (at 2,139 cm-1 in natrolite, 2,276 cm-1 in scolecite, and 2,176 and 2,259 cm-1 in mesolite) result from strong cation H2O Al Si framework interactions in NAT-type channels, and these bands can be used to evaluate the energetic evolution of Na?/Ca2? cations before and after phase transitions, especially for scolecite and mesolite. The 2,176 and 2,259 cm-1 absorption bands in mesolite also appear to be related to Na?/Ca2? order disorder that occur when mesolite loses its Ow4 H2O molecules.« less

VUV PHOTO-PROCESSING OF PAH CATIONS: QUANTITATIVE STUDY ON THE IONIZATION VERSUS FRAGMENTATION PROCESSES

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

Zhen, Junfeng; Castillo, Sarah Rodriguez; Joblin, Christine

2016-05-10

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

Single DNA molecules on freestanding and supported cationic lipid bilayers: diverse conformational dynamics controlled by the local bilayer properties

NASA Astrophysics Data System (ADS)

Herold, Christoph; Schwille, Petra; Petrov, Eugene P.

2016-02-01

We present experimental results on the interaction of DNA macromolecules with cationic lipid membranes with different properties, including freestanding membranes in the fluid and gel state, and supported lipid membranes in the fluid state and under conditions of fluid-gel phase coexistence. We observe diverse conformational dynamics of membrane-bound DNA molecules controlled by the local properties of the lipid bilayer. In case of fluid-state freestanding lipid membranes, the behaviour of DNA on the membrane is controlled by the membrane charge density: whereas DNA bound to weakly charged membranes predominantly behaves as a 2D random coil, an increase in the membrane charge density leads to membrane-driven irreversible DNA collapse and formation of subresolution-sized DNA globules. On the other hand, electrostatic binding of DNA macromolecules to gel-state freestanding membranes leads to completely arrested diffusion and conformational dynamics of membrane-adsorbed DNA. A drastically different picture is observed in case of DNA interaction with supported cationic lipid bilayers: When the supported bilayer is in the fluid state, membrane-bound DNA molecules undergo 2D translational Brownian motion and conformational fluctuations, irrespectively of the charge density of the supported bilayer. At the same time, when the supported cationic membrane shows fluid-gel phase coexistence, membrane-bound DNA molecules are strongly attracted to micrometre-sized gel-phase domains enriched with the cationic lipid, which results in 2D compaction of the membrane-bound macromolecules. This DNA compaction, however, is fully reversible, and disappears as soon as the membrane is heated above the fluid-gel coexistence. We also discuss possible biological implications of our experimental findings.

Mineral paragenesis on Mars: The roles of reactive surface area and diffusion

PubMed Central

Gil‐Lozano, Carolina; Uceda, Esther R.; Losa‐Adams, Elisabeth; Davila, Alfonso F.; Gago‐Duport, Luis

2017-01-01

Abstract Geochemical models of secondary mineral precipitation on Mars generally assume semiopen systems (open to the atmosphere but closed at the water‐sediment interface) and equilibrium conditions. However, in natural multicomponent systems, the reactive surface area of primary minerals controls the dissolution rate and affects the precipitation sequences of secondary phases, and simultaneously, the transport of dissolved species may occur through the atmosphere‐water and water‐sediment interfaces. Here we present a suite of geochemical models designed to analyze the formation of secondary minerals in basaltic sediments on Mars, evaluating the role of (i) reactive surface areas and (ii) the transport of ions through a basalt sediment column. We consider fully open conditions, both to the atmosphere and to the sediment, and a kinetic approach for mineral dissolution and precipitation. Our models consider a geochemical scenario constituted by a basin (i.e., a shallow lake) where supersaturation is generated by evaporation/cooling and the starting point is a solution in equilibrium with basaltic sediments. Our results show that cation removal by diffusion, along with the input of atmospheric volatiles and the influence of the reactive surface area of primary minerals, plays a central role in the evolution of the secondary mineral sequences formed. We conclude that precipitation of evaporites finds more restrictions in basaltic sediments of small grain size than in basaltic sediments of greater grain size. PMID:29104844

Mineral paragenesis on Mars: The roles of reactive surface area and diffusion.

PubMed

Fairén, Alberto G; Gil-Lozano, Carolina; Uceda, Esther R; Losa-Adams, Elisabeth; Davila, Alfonso F; Gago-Duport, Luis

2017-09-01

Geochemical models of secondary mineral precipitation on Mars generally assume semiopen systems (open to the atmosphere but closed at the water-sediment interface) and equilibrium conditions. However, in natural multicomponent systems, the reactive surface area of primary minerals controls the dissolution rate and affects the precipitation sequences of secondary phases, and simultaneously, the transport of dissolved species may occur through the atmosphere-water and water-sediment interfaces. Here we present a suite of geochemical models designed to analyze the formation of secondary minerals in basaltic sediments on Mars, evaluating the role of (i) reactive surface areas and (ii) the transport of ions through a basalt sediment column. We consider fully open conditions, both to the atmosphere and to the sediment, and a kinetic approach for mineral dissolution and precipitation. Our models consider a geochemical scenario constituted by a basin (i.e., a shallow lake) where supersaturation is generated by evaporation/cooling and the starting point is a solution in equilibrium with basaltic sediments. Our results show that cation removal by diffusion, along with the input of atmospheric volatiles and the influence of the reactive surface area of primary minerals, plays a central role in the evolution of the secondary mineral sequences formed. We conclude that precipitation of evaporites finds more restrictions in basaltic sediments of small grain size than in basaltic sediments of greater grain size.

Donnan membrane technique (DMT) for anion measurement.

PubMed

Vega, Flora Alonso; Weng, Liping; Temminghoff, Erwin J M; Van Riemsdijk, Willem H

2010-04-01

Donnan membrane technique (DMT) is developed and tested for determination of free anion concentrations. Time needed to reach the Donnan membrane equilibrium depends on type of ions and the background. The Donnan membrane equilibrium is reached in 1 day for Cl(-), 1-2 days for NO(3)(-), 1-4 days for SO(4)(2-) and SeO(4)(2-), and 1-14 days for H(2)PO(4)(-) in a background of 2-200 mM KCl or K(2)SO(4). The strongest effect of ionic strength on equilibrium time is found for H(2)PO(4)(-), followed by SO(4)(2-) and SeO(4)(2-), and then by Cl(-) and NO(3)(-). The negatively charged organic particles of fulvic and humic acids do not pass the membrane. Two approaches for the measurement of different anion species of the same element, such as SeO(4)(2-) and HSeO(3)(-), using DMT are proposed and tested. These two approaches are based on transport kinetics or response to ionic strength difference. A transport model that was developed previously for cation DMT is applied in this work to analyze the rate-limiting step in the anion DMT. In the absence of mobile/labile complexes, transport tends to be controlled by diffusion in solution at a low ionic strength, whereas at a higher ionic strength, diffusion in the membrane starts to control the transport.

Understanding the Alteration of Bentonite Backfill Using Coupled THMC Modeling for a Long Term Heater Test at the Grimsel Underground Research Lab

NASA Astrophysics Data System (ADS)

Birkholzer, J. T.; Zheng, L.; Xu, H.; Rutqvist, J.

2017-12-01

Compacted bentonite is commonly used as backfill material in emplacement tunnels of nuclear waste repositories because of its low permeability, high swelling pressure, and retardation capacity of radionuclide. To assess whether this backfill material can maintain these favorable features when undergoing heating from the waste package and hydration from the host rock, we need a thorough understanding of the thermal, hydrological, mechanical, and chemical evolution of bentonite under disposal conditions. Dedicated field tests integrated with THMC modeling provide an effective way to deepen such understanding. Here, we present coupled THMC models for an in situ heater test which was conducted at the Grimsel Test Site in Switzerland for 18 years. The comprehensive monitoring data obtained in the test provide a unique opportunity to evaluate bentonite integrity and test coupled THMC models. We developed a modeling strategy where conceptual model complexity is increased gradually by adding/testing processes such as Non-Darcian flow, enhanced vapor diffusion, thermal osmosis and different constitutive relationships for permeability/porosity changes due to swelling. The final THMC model explains well all the THM data and the concentration profiles of conservative chemical species. Over the course of modeling the in situ test, we learned that (1) including Non-Darcian flow into the model leads to a significant underestimation of hydration rate of bentonite, (2) chemical data provide an important additional piece of information for calibrating a THM model; (3) key processes needed to reproduce the data include vapor diffusion, as well as porosity and permeability changes due to swelling and thermal osmosis; (4) the concentration profiles of cations (calcium, potassium, magnesium and sodium) were largely shaped by transport processes despite their concentration levels being affected by mineral dissolution/precipitation and cation exchange. The concentration profiles of pH, bicarbonate and sulphate were largely determined by chemical reactions. These findings enable more reliable calculation of the time frame and condition of the early unsaturated phase in bentonite, the porosity and permeability after the bentonite becomes fully saturated, and how transport processes interact with reactions.

Diffusion Rates of Organic Molecules in Secondary Organic Aerosol Particle

NASA Astrophysics Data System (ADS)

Bertram, A. K.; Chenyakin, Y.; Song, M.; Grayson, J. W.; Ullmann, D.; Evoy, E.; Renbaum-Wolff, L.; Liu, P.; Zhang, Y.; Kamal, S.; Martin, S. T.

2016-12-01

Information on the diffusion rates of organic molecules in secondary organic aerosol (SOA) particles are needed when predicting their size distribution, growth rates, photochemistry and heterogeneous chemistry. We have used two approaches to determine diffusion rates of organic molecules in SOA particles and proxies of SOA. In the first approach, we measured viscosities and then predicted diffusion rates using the Stokes-Einstein relation. In the second approach, we measured diffusion rates directly using a technique referred to as fluorescence recovery after photobleaching. Results from these measurements, including diffusion coefficients as a function of water activity, will be presented and the implications discussed.

Excimer Formation Dynamics of Dipyrenyldecane in Structurally Different Ionic Liquids.

PubMed

Yadav, Anita; Pandey, Siddharth

2017-12-07

Ionic liquids, being composed of ions alone, may offer alternative pathways for molecular aggregation. These pathways could be controlled by the chemical structure of the cation and the anion of the ionic liquids. Intramolecular excimer formation dynamics of a bifluorophoric probe, 1,3-bis(1-pyrenyl)decane [1Py(10)1Py], where the fluorophoric pyrene moieties are separated by a long decyl chain, is investigated in seven different ionic liquids in 10-90 °C temperature range. The long alkyl separator allows for ample interaction with the solubilizing milieu prior to the formation of the excimer. The ionic liquids are composed of two sets, one having four ionic liquids of 1-butyl-3-methylimidazolium cation ([bmim + ]) with different anions and the other having four ionic liquids of bis(trifluoromethylsulfonyl)imide anion ([Tf 2 N - ]) with different cations. The excimer-to-monomer emission intensity ratio (I E /I M ) is found to increase with increasing temperature in sigmoidal fashion. Chemical structure of the ionic liquid controls the excimer formation efficiency, as I E /I M values within ionic liquids with the same viscosities are found to be significantly different. The excited-state intensity decay kinetics of 1Py(10)1Py in ionic liquids do not adhere to a simplistic Birk's scheme, where only one excimer conformer forms after excitation. The apparent rate constants of excimer formation (k a ) in highly viscous ionic liquids are an order of magnitude lower than those reported in organic solvents. In general, the higher the viscosity of the ionic liquid, the more sensitive is the k a to the temperature with higher activation energy, E a . The trend in E a is found to be similar to that for activation energy of the viscous flow (E a,η ). Stokes-Einstein relationship is not followed in [bmim + ] ionic liquids; however, with the exception of [choline][Tf 2 N], it is found to be followed in [Tf 2 N - ] ionic liquids suggesting the cyclization dynamics of 1Py(10)1Py to be diffusion-controlled and to depend on the viscosity of the ionic liquid irrespective of the identity of the cation. The dependence of ionic liquid structure on cyclization dynamics to form intramolecular excimer is amply highlighted.

Distinguishing Biologically Relevant Hexoses by Water Adduction to the Lithium-Cationized Molecule.

PubMed

Campbell, Matthew T; Chen, Dazhe; Wallbillich, Nicholas J; Glish, Gary L

2017-10-03

A method to distinguish the four most common biologically relevant underivatized hexoses, d-glucose, d-galactose, d-mannose, and d-fructose, using only mass spectrometry with no prior separation/derivatization step has been developed. Electrospray of a solution containing hexose and a lithium salt generates [Hexose+Li] + . The lithium-cationized hexoses adduct water in a quadrupole ion trap. The rate of this water adduction reaction can be used to distinguish the four hexoses. Additionally, for each hexose, multiple lithiation sites are possible, allowing for multiple structures of [Hexose+Li] + . Electrospray produces at least one structure that reacts with water and at least one that does not. The ratio of unreactive lithium-cationized hexose to total lithium-cationized hexose is unique for the four hexoses studied, providing a second method for distinguishing the isomers. Use of the water adduction reaction rate or the unreactive ratio provides two separate methods for confidently (p ≤ 0.02) distinguishing the most common biologically relevant hexoses using only femtomoles of hexose. Additionally, binary mixtures of glucose and fructose were studied. A calibration curve was created by measuring the reaction rate of various samples with different ratios of fructose and glucose. The calibration curve was used to accurately measure the percentage of fructose in three samples of high fructose corn syrup (<4% error).

Theoretical and computational studies of renewable energy materials: Room temperature ionic liquids and proton exchange membranes

NASA Astrophysics Data System (ADS)

Feng, Shulu

2011-12-01

Two kinds of renewable energy materials, room temperature ionic liquids (RTILs) and proton exchange membranes (PEMs), especially Nafion, are studied by computational and theoretical approaches. The ultimate purpose of the present research is to design novel materials to meet the future energy demands. To elucidate the effect of alkyl side chain length and anion on the structure and dynamics of the mixtures, molecular dynamics (MD) simulations of three RTILs/water mixtures at various water mole fractions: 1-butyl-3-methylimidazolium (BMIM+)/BF4-, 1-octyl-3-methylimidazolium (OMIM+)/BF4-, and OMIM +/Cl- are performed. Replacing the BMIM + cation with OMIM+ results in stronger aggregation of the cations as well as a slower diffusion of the anions, and replacing the BF4- anion with Cl- alters the water distribution at low water mole fractions and slows diffusion of the mixtures. Potential experimental manifestations of these behaviors in both cases are provided. Proton solvation properties and transport mechanisms are studied in hydrated Nafion, by using the self-consistent multistate empirical valence bond (SCI-MS-EVB) method. It is found that by stabilizing a more Zundel-like (H5O 2+) structure in the first solvation shells, the solvation of excess protons, as well as the proton hydration structure are both influenced by the sulfonate groups. Hydrate proton-related hydrogen bond networks are observed to be more stable than those with water alone. In order to characterize the nature of the proton transport (PT), diffusive motion, Arrhenius activation energies, and transport pathways are calculated and analyzed. Analysis of diffusive motion suggests that (1) a proton-hopping mechanism dominates the proton transport for the studied water loading levels and (2) there is an obvious degree of anti-correlation between the proton hopping and the vehicular transport. The activation energy drops rapidly with an increasing water content when the water loading level is smaller than ˜ 10 H2O/SO 3-, which is consistent with experimental observations. The sulfonate groups are also found to have influence on the proton hopping directions. The temperature and water content effects on the PT pathways are also investigated. The morphological effects on proton solvation and transport in hydrated Nafion are investigated, by using the SCI-MS-EVB method. Two of the most significant morphological models of Nafion, the lamellar model and the cylinder model, are selected. The two models exhibit distinct PT patterns, which result in different proton diffusion rates. In both models, the interaction between protons and the sulfonate groups are proven to be the key to determining PT behavior. The proton solvation structure change as a function of the distance between protons and sulfonate groups has been analyzed. It is found that the increase of water cylinder radius or water layer height leads to the presence of more protons around the sulfonate groups. Furthermore, at a lower hydration level, the increased amount of protons around the sulfonate groups consists of more Zundel-like structures, which is influenced by the distinct morphological structures of Nafion.

Grounding electrode and method of reducing the electrical resistance of soils

DOEpatents

Koehmstedt, Paul L.

1980-01-01

A first solution of an electrolyte is injected underground into a volume of soil having negative surface charges on its particles. A cationic surfactant suspended in this solution neutralizes these surface charges of the soil particles within the volume. Following the first solution, a cationic asphalt emulsion suspended in a second solution is injected into the volume. The asphalt emulsion diffuses through the volume and electrostatically bonds with additional soil surrounding the volume such that an electrically conductive water repellant shell enclosing the volume is formed. This shell prevents the leaching of electrolyte from the volume into the additional soil. The second solution also contains a dissolved deliquescent salt which draws water into the volume prior to the formation of the shell. When electrically connected to an electrical installation such as a power line tower, the volume constitutes a grounding electrode for the tower.

Quantum chemistry and excited states: First investigations on pyrene-like molecules

NASA Technical Reports Server (NTRS)

Parisel, Olivier; Ellinger, Y.

1994-01-01

Although the calculations are expected to be accurate within 10%, it follows then that there cannot be proposed unquestionable one-to-one attribution due to the density of the DIB's (Diffuse Interstellar Bands). Nevertheless, it has been shown that if one is interested in the experimental study of methyl-pyrene cations, for example, then, the most promising candidate is the 1-methyl isomer: this isomer has been investigated by d'Hendecourt and Leger (1993,1994) and their spectrum shows very striking features in very good agreement with both our calculations and a few DIB's. However, 1-methyl-pyrene cation is not the only product susceptible of being formed in this experiment, and further investigations are in progress to give a complete interpretations of the results. This preliminary report on pyrene-like molecules illustrates the role that theoretical calculations can ply in both the design and the interpretation of experiments.

Adsorption of anionic and cationic dyes on activated carbon from aqueous solutions: equilibrium and kinetics.

PubMed

Rodríguez, Araceli; García, Juan; Ovejero, Gabriel; Mestanza, María

2009-12-30

Activated carbon was utilized as adsorbent to remove anionic dye, Orange II (OII), and cationic dye, Methylene blue (MB), from aqueous solutions by adsorption. Batch experiments were conducted to study the effects of temperature (30-65 degrees C), initial concentration of adsorbate (300-500 mg L(-1)) and pH (3.0-9.0) on dyes adsorption. Equilibrium adsorption isotherms and kinetics were investigated. The equilibrium experimental data were analyzed by the Langmuir, Freundlich, Toth and Redlich-Peterson models. The kinetic data obtained with different carbon mass were analyzed using a pseudo-first order, pseudo-second order, intraparticle diffusion, Bangham and Chien-Clayton equations. The best results were achieved with the Langmuir isotherm equilibrium model and with the pseudo-second order kinetic model. The activated carbon was found to be very effective as adsorbent for MB and OII from aqueous solutions.

Targeted drug delivery across the blood brain barrier in Alzheimer's disease.

PubMed

Rocha, Sandra

2013-01-01

The discovery of drugs for Alzheimer's disease (AD) therapy that can also permeate the blood brain barrier (BBB) is very difficult owing to its specificity and restrictive nature. The BBB disruption or the administration of the drug directly into the brain is not an option due to toxic effects and low diffusion of the therapeutic molecule in the brain parenchyma. A promising approach for drug systemic delivery to the central nervous system is the use of nanosized carriers. The therapeutic potential of certain nanopharmaceuticals for AD has already been demonstrated in vivo after systemic delivery. They are based on i) conjugates of drug and monoclonal antibodies against BBB endogenous receptors; ii) cationized or end terminal protected proteins/peptides; iii) liposomes and polymeric nanoparticles coated with polysorbate 80, cationic macromolecules or antibodies against BBB receptors/amyloid beta-peptides. Optimization and further validation of these systems are needed.

Interactions between water and 1-butyl-1-methylpyrrolidinium ionic liquids

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

Fadeeva, Tatiana A.; DeVine, Jessalyn A.; Castner, Edward W., E-mail: ed.castner@rutgers.edu

2015-08-14

We report experimental results on the diffusivity of water in two ionic liquids obtained using the pulsed-gradient spin-echo NMR method. Both ionic liquids have the same cation, 1-butyl-1-methylpyrrolidinium, but different trifluoromethyl-containing anions. One has a strongly hydrophobic anion, bis(trifluoromethylsulfonyl)amide, while the second has a hydrophilic anion, trifluoromethylsulfonate. Transport of water in these ionic liquids is much faster than would be predicted from hydrodynamic laws, indicating that the neutral water molecules experience a very different friction than the anions and cations at the molecular level. Temperature-dependent viscosities, conductivities, and densities are reported as a function of water concentration to further analyzemore » the properties of the ionic liquid-water mixtures. These results on the properties of water in ionic liquids should be of interest to researchers in diverse areas ranging from separations, solubilizing biomass and energy technologies.« less

Descriptors for ions and ion-pairs for use in linear free energy relationships.

PubMed

Abraham, Michael H; Acree, William E

2016-01-22

The determination of Abraham descriptors for single ions is reviewed, and equations are given for the partition of single ions from water to a number of solvents. These ions include permanent anions and cations and ionic species such as carboxylic acid anions, phenoxide anions and protonated base cations. Descriptors for a large number of ions and ionic species are listed, and equations for the prediction of Abraham descriptors for ionic species are given. The application of descriptors for ions and ionic species to physicochemical processes is given; these are to water-solvent partitions, HPLC retention data, immobilised artificial membranes, the Finkelstein reaction and diffusion in water. Applications to biological processes include brain permeation, microsomal degradation of drugs, skin permeation and human intestinal absorption. The review concludes with a section on the determination of descriptors for ion-pairs. Copyright © 2015 Elsevier B.V. All rights reserved.

Synthesis, structures and properties of three copper complexes with dibutyldithiocarbamate ligand

NASA Astrophysics Data System (ADS)

Wang, Chen; Niu, Jiao; Li, Jun; Ma, Xiaoxun

2017-05-01

Three copper complexes constructed with sulfur-containing dibutyldithiocarbamate ligand (DDTC), [(Et2NCS2)4Cu2] (1), [(Et2NCS2)(EtO)Cu]2 (2) and [(Et2NCS2)6Cu13I10]n (3) have been synthesized through the reaction of CuI with different mole ratios of DDTC under solution-diffusion conditions. The single crystal X-ray diffraction revealed that divalent Cu cations in complexes 1 and 2 imply that the reactant, Cu(I), was involved in the redox process. They formed binuclear complexes according to bridging S from DDTC ligands and O atoms from ethanol molecules respectively. The mixed valence Cu cations had two types of coordination environments in complex 3 and formed a two-dimensional layered coordination polymer by bridging the five-core Cu(I) clusters and Cu(II). The powder X-ray diffraction, luminescent, thermogravimetric analysis, etc. were also studied in this paper.

Effects of silicate weathering on water chemistry in forested, upland, felsic terrane of the USA

NASA Astrophysics Data System (ADS)

Stauffer, Robert E.; Wittchen, Bruce D.

1991-11-01

We use data from the US EPA National Surface Water Survey (NSWS), the USGS Bench-Mark Station monitoring program, and the National Acid Deposition Program (NADP) to evaluate the role of weathering in supplying base cations to surface waters in forested, upland, felsic terrane of the northeastern, northcentral, and northwestern (Idaho batholith) United States. Multivariate regression reveals differential effects of discharge on individual base cations and silica, but no secular trend in the Ca/Na denudation rate over 24 yr (1965-1988) for the Wild River catchment in the White Mountains. Because the turn-over time for Na in the soil-exchange complex is only ca. 1.5 yr, the long-term behavior of the ratios Ca/Na and Si/Na in waters leaving this catchment indicates that weathering is compensating for base cation export. In every subregion, Ca and Mg concentrations in lakes are statistically linked to nonmarine Na, but the median Ca/Na ratio is greater than the ratio in local plagioclase. We attribute this inequality to nonstoichiometric weathering of calcium in juvenile (formerly glaciated) terrane, not to leaching of exchangeable cations by SO 4, because intraregional and cross-regional statistical analysis reveals no effect of atmospherically derived sulfate ion. The median base cation denudation rates (meq m -2 yr -1) for these American lake regions are: Maine granites (108); western Adirondack felsic gneiss (85); Vermilion batholith (42); Idaho batholith (52). The regional rates are high enough to compensate for present wet deposition of acidifying anions except in some vulnerable lake watersheds in the western Adirondacks.

Multicomponent transport in membranes for redox flow batteries

NASA Astrophysics Data System (ADS)

Monroe, Charles

2015-03-01

Redox flow batteries (RFBs) incorporate separator membranes, which ideally prevent mixing of electrochemically active species while permitting crossover of inactive supporting ions. Understanding crossover and membrane selectivity may require multicomponent transport models that account for solute/solute interactions within the membrane, as well as solute/membrane interactions. Application of the Onsager-Stefan-Maxwell formalism allows one to account for all the dissipative phenomena that may accompany component fluxes through RFB membranes. The magnitudes of dissipative interactions (diffusional drag forces) are quantified by matching experimentally established concentration transients with theory. Such transients can be measured non-invasively using DC conductometry, but the accuracy of this method requires precise characterization of the bulk RFB electrolytes. Aqueous solutions containing both vanadyl sulfate (VOSO4) and sulfuric acid (H2SO4) are relevant to RFB technology. One of the first precise characterizations of aqueous vanadyl sulfate has been implemented and will be reported. To assess the viability of a separator for vanadium RFB applications with cell-level simulations, it is critical to understand the tendencies of various classes of membranes to absorb (uptake) active species, and to know the relative rates of active-species and supporting-electrolyte diffusion. It is also of practical interest to investigate the simultaneous diffusion of active species and supports, because interactions between solutes may ultimately affect the charge efficiency and power efficiency of the RFB system as a whole. A novel implementation of Barnes's classical model of dialysis-cell diffusion [Physics 5:1 (1934) 4-8] is developed to measure the binary diffusion coefficients and sorption equilibria for single solutes (VOSO4 or H2SO4) in porous membranes and cation-exchange membranes. With the binary diffusion and uptake measurement in hand, a computer simulation that extends the approach of Heintz, Wiedemann and Ziegler [J. Membrane Science 137:1-2 (1997) 121-132] is used to establish Onsager resistances that describe the drag forces VOSO4 and H2SO4 exert on each other as they interdiffuse. The ramifications of these interactions for different classes of membranes - and for RFB applications - will be discussed. NSF CBET-1253544.

Generating a Simulated Fluid Flow Over an Aircraft Surface Using Anisotropic Diffusion

NASA Technical Reports Server (NTRS)

Rodriguez, David L. (Inventor); Sturdza, Peter (Inventor)

2013-01-01

A fluid-flow simulation over a computer-generated aircraft surface is generated using a diffusion technique. The surface is comprised of a surface mesh of polygons. A boundary-layer fluid property is obtained for a subset of the polygons of the surface mesh. A pressure-gradient vector is determined for a selected polygon, the selected polygon belonging to the surface mesh but not one of the subset of polygons. A maximum and minimum diffusion rate is determined along directions determined using a pressure gradient vector corresponding to the selected polygon. A diffusion-path vector is defined between a point in the selected polygon and a neighboring point in a neighboring polygon. An updated fluid property is determined for the selected polygon using a variable diffusion rate, the variable diffusion rate based on the minimum diffusion rate, maximum diffusion rate, and angular difference between the diffusion-path vector and the pressure-gradient vector.

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

PubMed Central

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

2016-01-01

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

Effect of Ion Rigidity on Physical Properties of Ionic Liquids Studied by Molecular Dynamics Simulation.

PubMed

Ramírez-González, Pedro E; Ren, Gan; Saielli, Giacomo; Wang, Yanting

2016-06-30

In this work, we have performed molecular dynamics (MD) simulations to compare the structural and dynamical properties of three ionic liquids (ILs), 1-ethyl-3-methyl-imidazolium tetrafluorborate ([EMI(+)][BF4(-)]), 1,1'-dimethyl-4,4'-bipyridinium bis(tetrafluorborate) ([VIO(2+)][BF4(-)]2), and 1,1'-dimethyl-4,4'-bipyridinium bis(trifluoromethylsulfonyl)imide (bistriflimide in short) ([VIO(2+)][Tf2N(-)]2), aiming to discover the influence of ion rigidity on the physical properties of ILs. [VIO(2+)] is more rigid than [EMI(+)], and [BF4(-)] is more rigid than [Tf2N(-)]. [VIO(2+)][BF4(-)]2 has an anion distribution different from the other two by the higher and sharper peaks in the cation-anion radial distribution functions, reflecting a close-packed local structure of anions around cations. [VIO(2+)][BF4(-)]2 and [VIO(2+)][Tf2N(-)]2 have similar dynamics much slower than [EMI(+)][BF4(-)], and [VIO(2+)][Tf2N(-)]2 shows a more isotropic molecular distribution than [VIO(2+)][BF4(-)]2 and [EMI(+)][BF4(-)]. Additionally, we have simulated two modified viologen-based ILs to reinforce our interpretations. We conclude from the above simulation results that the rigidity of anions influences the alignment of cations and that the rigidity of cations shows a large obstacle to their rotational capacity. Moreover, we have observed a slower diffusion of [VIO(2+)][BF4(-)]2 due to the electrostatic correlations, which stabilizes the ion-cage effect.

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

DOE PAGES

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

2017-07-24

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

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

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

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

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

Characterization of two cation diffusion facilitators NpunF0707 and NpunF1794 in Nostoc punctiforme.

PubMed

Hudek, L; Pearson, L; Michalczyk, A A; Bräu, L; Neilan, B A; Ackland, M L

2015-11-01

To characterize genes involved in maintaining homeostatic levels of zinc in the cyanobacterium Nostoc punctiforme. Metal efflux transporters play a central role in maintaining homeostatic levels of trace elements such as zinc. Sequence analyses of the N. punctiforme genome identified two potential cation diffusion facilitator (CDF) metal efflux transporters, Npun_F0707 (Cdf31) and Npun_F1794 (Cdf33). Deletion of either Cdf31or Cdf33 resulted in increased zinc retention over 3 h. Interestingly, Cdf31(-) and Cdf33(-) mutants showed no change in sensitivity to zinc exposure in comparison with the wild type, suggesting some compensatory capacity for the loss of each other. Using qRT-PCR, a possible interaction was observed between the two cdf's, where the Cdf31(-) mutant had a more profound effect on cdf33 expression than Cdf33(-) did on cdf31. Over-expression of Cdf31 and Cdf33 in ZntA(-) - and ZitB(-) -deficient Escherichia coli revealed function similarities between the ZntA and ZitB of E. coli and the cyanobacterial transporters. The data presented shed light on the function of two important transporters that regulate zinc homeostasis in N. punctiforme. This study shows for the first time the functional characterization of two cyanobacterial zinc efflux proteins belonging to the CDF family. © 2015 The Society for Applied Microbiology.

Optical (diffuse reflectance) and Mossbauer spectroscopic study of nontronite and related Fe-bearing smectites

USGS Publications Warehouse

Sherman, David M.; Vergo, N.

1988-01-01

Near-ultraviolet to near-infrared optical (diffuse reflectance) spectra of several nontronites and related Fe-bearing smectites [(Fe2+,Fe3+)-bearing saponite and (Fe2+,Fe3+)-bearing montmorillonite] are presented and interpreted. Mossbauer spectra at 298 K are also presented to help interpret the optical spectra. The optical spectra of nontronites are dominated by the ligand field transitions of Fe3+ in octahedral coordination sites. In addition to the ligand field transitions of single Fe3+ cations, a broad absorption band centered near 22000 cm-1 is observed that may be due to the simultaneous excitation of two Fe3+ cations to the 4T1g (4G) state. Alternatively, this band may represent excitations to the 2A2g and 2T1g ligand field states. For most samples, the amount of tetrahedrally coordinated Fe3+ was below that detectable by Mossbauer spectroscopy (1-3% of total Fe). However, the optical spectra of all of the nontronites show an absorption band near 23000 cm-1. This band is assigned to the 6A1 ??? 4E,4A1 transition of tetrahedrally coordinated Fe3+. The optical spectra of mixed-valence Fe-bearing smectites show a broad absorption band at 14000-15000 cm-1 owing to Fe2+ ??? Fe3+ charge transfer. -from Authors

Bulk deposition of base cationic nutrients in China's forests: Annual rates and spatial characteristics

Treesearch

Enzai Du; Wim de Vries; Steven McNulty; Mark E. Fenn

2018-01-01

Base cations, such as potassium (K+), calcium (Ca2+) and magnesium (Mg2+), are essential nutrients for plant growth and their atmospheric inputs can buffer the effect of acid deposition by nitrogen (N) and sulphur (S) compounds. However, the spatial variation in atmospheric deposition of these base...

Use of polyurethane foam and 3-hydroxy-7,8-benzo-1,2,3,4-tetrahydroquinoline for determination of nitrite by diffuse reflectance spectroscopy and colorimetry.

PubMed

Apyari, V V; Dmitrienko, S G; Ostrovskaya, V M; Anaev, E K; Zolotov, Y A

2008-07-01

Polyurethane foam (PUF) has been suggested as a solid polymeric reagent for determination of nitrite. The determination is based on the diazotization of end toluidine groups of PUF with nitrite in acidic medium followed by coupling of polymeric diazonium cation with 3-hydroxy-7,8-benzo-1,2,3,4-tetrahydroquinoline. The intensely colored polymeric azodye formed in this reaction can be used as a convenient analytic form for the determination of nitrite by diffuse reflectance spectroscopy (c (min) = 0.7 ng mL(-1)). The possibility of using a desktop scanner, digital camera, and computer data processing for the numerical evaluation of the color intensity of the polymeric azodye has been investigated. A scanner and digital camera can be used for determination of nitrite with the same sensitivity and reproducibility as with diffuse reflectance spectroscopy. The approach developed was applied for determination of nitrite in river water and human exhaled breath condensate.

Atomistic modeling of La3+ doping segregation effect on nanocrystalline yttria-stabilized zirconia.

PubMed

Zhang, Shenli; Sha, Haoyan; Castro, Ricardo H R; Faller, Roland

2018-05-16

The effect of La3+ doping on the structure and ionic conductivity change in nanocrystalline yttria-stabilized zirconia (YSZ) was studied using a combination of Monte Carlo and molecular dynamics simulations. The simulation revealed the segregation of La3+ at eight tilt grain boundary (GB) structures and predicted an average grain boundary (GB) energy decrease of 0.25 J m-2, which is close to the experimental values reported in the literature. Cation stabilization was found to be the main reason for the GB energy decrease, and energy fluctuations near the grain boundary are smoothed out with La3+ segregation. Both dynamic and energetic analysis on the Σ13(510)/[001] GB structure revealed La3+ doping hinders O2- diffusion in the GB region, where the diffusion coefficient monotonically decreases with increasing La3+ doping concentration. The effect was attributed to the increase in the site-dependent migration barriers for O2- hopping caused by segregated La3+, which also leads to anisotropic diffusion at the GB.

Process and apparatus for recovery of fissionable materials from spent reactor fuel by anodic dissolution

DOEpatents

Tomczuk, Zygmunt; Miller, William E.; Wolson, Raymond D.; Gay, Eddie C.

1991-01-01

An electrochemical process and apparatus for the recovery of uranium and plutonium from spent metal clad fuel pins is disclosed. The process uses secondary reactions between U.sup.+4 cations and elemental uranium at the anode to increase reaction rates and improve anodic efficiency compared to prior art processes. In another embodiment of the process, secondary reactions between Cd.sup.+2 cations and elemental uranium to form uranium cations and elemental cadmium also assists in oxidizing the uranium at the anode.

Ionomers for Ion-Conducting Energy Materials

NASA Astrophysics Data System (ADS)

Colby, Ralph

For ionic actuators and battery separators, it is vital to utilize single-ion conducting ionomers that avoid the detrimental polarization of other ions. Single-ion conducting ionomers are synthesized based on DFT calculations, with low glass transition temperatures (facile dynamics) to prepare ion-conducting membranes for battery separators that conduct Li+ or Na+. Characterization by X-ray scattering, dielectric spectroscopy, FTIR, NMR and linear viscoelasticity collectively develop a coherent picture of ionic aggregation and both counterion and polymer dynamics. 7Li NMR diffusion measurements find that diffusion is faster than expected by conductivity using the Nernst-Einstein equation, which means that the majority of Li diffusion occurs by ion pairs moving with the polymer segmental motion. Segmental motion only contributes to ionic conduction in the rare event that one of these ion pairs has an extra Li (a positive triple ion). This leads us to a new metric for ion-conducting soft materials, the product of the cation number density p0 and their diffusion coefficient D; p0D is the diffusive flux of lithium ions. This new metric has a maximum at intermediate ion content that corresponds to the overlap of ion pair polarizability volumes. At higher ion contents, the ion pairs interact strongly and form larger aggregation states that retard segmental motion of both mobile ion pairs and triple ions.

Generating a Simulated Fluid Flow over a Surface Using Anisotropic Diffusion

NASA Technical Reports Server (NTRS)

Rodriguez, David L. (Inventor); Sturdza, Peter (Inventor)

2016-01-01

A fluid-flow simulation over a computer-generated surface is generated using a diffusion technique. The surface is comprised of a surface mesh of polygons. A boundary-layer fluid property is obtained for a subset of the polygons of the surface mesh. A gradient vector is determined for a selected polygon, the selected polygon belonging to the surface mesh but not one of the subset of polygons. A maximum and minimum diffusion rate is determined along directions determined using the gradient vector corresponding to the selected polygon. A diffusion-path vector is defined between a point in the selected polygon and a neighboring point in a neighboring polygon. An updated fluid property is determined for the selected polygon using a variable diffusion rate, the variable diffusion rate based on the minimum diffusion rate, maximum diffusion rate, and the gradient vector.

Radionuclide migration in clayrock host formations for deep geological disposal of radioactive waste: advances in process understanding and up-scaling methods resulting from the EC integrated project `Funmig

NASA Astrophysics Data System (ADS)

Altmann, S.; Tournassat, C.; Goutelard, F.; Parneix, J. C.; Gimmi, T.; Maes, N.

2009-04-01

One of the ‘pillars' supporting Safety Cases for deep geological disposal of radioactive waste in clayrock formations is the knowledge base regarding radionuclide (Rn) retention by sorption and diffusion-driven transport which is why the EC integrated project ‘Funmig' focused a major part of its effort on advancing understanding of these two macroscopic phenomena. This talk presents some of the main results of this four year effort (2005-2008). One of the keys to understanding diffusion-driven transport of anionic and cationic radionuclide species in clayrocks lies in a detailed understanding of the phenomena governing Rn total concentration and speciation (dissolved, adsorbed) in the different types of pore spaces present in highly-compacted masses of permanently charged clay minerals. Work carried out on a specifically synthesized montmorillonite (a model for the clay mineral fraction in clayrocks) led to development, and preliminary experimental validation, of a conceptually coherent set of theoretical models (molecular dynamics, electrostatic double layer, thermodynamic) describing dissolved ion and water solvent behavior in this material. This work, complemented by the existing state of the art, provides a sound theoretical basis for explaining such important phenomena as anion exclusion, cation exchange and the diffusion behavior of anions, weakly sorbing cations and water tracers. Concerning the behavior of strongly sorbing and/or redox-reactive radionuclides in clay systems, project research improved understanding of the nature of sorption reactions and sorbed species structure for key radioelements, or analogues (U, Se, Eu, Sm, Yb, Nd) on the basal surfaces and in the interlayers of synthetic or purified clay minerals. A probable mechanism for Se(IV) retention by reduction to Se° in Fe2+-containing clays was brought to light; this same process was also studied on the Callovo-Oxfordien clayrock targeted by the French radwaste management program. The migration of most radionuclides in clayrocks, in particular the actinides, is limited by their strong sorption on rock mineral surfaces. Much effort was devoted in Funmig to improving understanding of this process on the clayrocks being studied in the Swiss, Belgian and French radwaste management programs. Specific attention was focused on (i) elucidating the effect of dissolved organic matter on Am(III), Th(IV), Eu(III) sorption on clayrock surfaces and (ii) determining the link between Kd measured on dispersed rock systems and the Kd operant in intact rock volumes, i.e. during diffusion. Regarding the latter question, results indicate that Kd values for ‘dispersed' and ‘intact' materials are quite similar for certain elements (Na, Sr, Cs, Co). On the other hand, Kd values obtained by modeling results of diffusion experiments involving strongly sorbing elements as Cs, Co and Eu were always significantly smaller than those predicted based on sorption data measured in corresponding batch systems. This is an area where additional research is being planned. A major effort was devoted to improving understanding of the effects of small-scale (m to cm) clayrock structure and large-scale (dm to hm) mineralogical composition on radionuclide diffusion-retention. The program focusing on the small-scale produced a method for simulating the results of tracer diffusion in an intact rock based on the actual rock microstructure of the rock sample to be used in the diffusion experiment. This model was used to predict / inverse model the spatial distribution of highly sorbing tracers (Eu, Cu). This overall approach is also being used to understand how changes in mineralogical composition can affect the values of macroscopic diffusion parameters (De, tortuosity, anisiotropy). At a much larger scale, the results of (i) a geostatistical analysis of clayrock mineralogical variability and (ii) measurements of De and Kd dependence on mineralogy for Cs and Cl, were combined to create models of parameter variability at the formation scale. These models were used to evaluate the effects of formation scale heterogeneity on predictive modeling of radionuclide migration. Measurements and modeling of natural tracer profiles were also carried out in order to evaluate the diffusion characteristics at geological time and space scales.

Measurement of cation exchange capacity (CEC) on natural zeolite by percolation method

NASA Astrophysics Data System (ADS)

Wiyantoko, Bayu; Rahmah, Nafisa

2017-12-01

The cation exchange capacity (CEC)measurement has been carried out in natural zeolite by percolation method. The natural zeolite samples used for cation exchange capacity measurement were activated beforehand with physical activation and chemical activation. The physically activated zeolite was done by calcination process at 600 °C for 4 hours. The natural zeolite was activated chemically by using sodium hydroxide by refluxing process at 60-80 °C for 3 hours. In summary, cation exchange capacity (CEC) determination was performed by percolation, distillation and titration processes. Based on the measurement that has been done, the exchange rate results from physical activated and chemical activated of natural zeolite were 181.90cmol (+)/kg and 901.49cmol (+)/kg respectively.

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

NASA Technical Reports Server (NTRS)

Ganguly, Jibamitra

1989-01-01

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

Surface area of montmorillonite from the dynamic sorption of nitrogen and carbon dioxide

USGS Publications Warehouse

Thomas, Josephus; Bohor, Bruce F.

1968-01-01

Surface area determinations were made on a montmorillonite with various cations emplaced on the exchangeable sites, utilizing nitrogen and carbon dioxide as adsorbates at 77°K and 195°K, respectively, in a dynamic system. From the fraction of a Mississippi montmorillonite less than about 1 μ in size, samples were prepared by replacing the original exchangeable cations with Li+, Na+, K+, Rb+, Cs+, Mg++, Ca++, Ba++, and NH4+, forming a series of homoionic montmorillonite species.Surface areas from 3-point B.E.T. plots (half-hour adsorption points), with nitrogen as the adsorbate, ranged from 61 m2/g for Li-montmorillonite to 138 m2/g for Cs-montmorillonite, thus reflecting a certain degree of nitrogen penetration between layers. Complete penetration should theoretically result in a surface area of over 300 m2/g for this clay with a nitrogen monolayer between each pair of platelets. The experimental data indicate that the extent of penetration is time-dependent and is also a function of the interlayer forces as governed by the size and charge of the replaceable cation. This finding negates the generally accepted concept that nitrogen at 77°K does not penetrate the layers and provides a measure only of the external surface of expandable clay minerals.A further measure of the variation of interlayer forces is provided by the adsorption of carbon dioxide at 195°K. Surface area values ranged from 99 m2/g for Li-montmorillonite to 315 m2/g for Csmontmorillonite. Although the carbon dioxide molecule is larger than the nitrogen molecule, its greater penetration apparently is a result of its being kinetically more energetic (with a larger diffusion coefficient) at its higher adsorption temperature. Similar differences have been found with both adsorbates in the study of microporous substances, such as coal, where activated diffusion is of considerable significance.

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

NASA Astrophysics Data System (ADS)

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

2010-05-01

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

Using light transmission to watch hydrogen diffuse

PubMed Central

Pálsson, Gunnar K.; Bliersbach, Andreas; Wolff, Max; Zamani, Atieh; Hjörvarsson, Björgvin

2012-01-01

Because of its light weight and small size, hydrogen exhibits one of the fastest diffusion rates in solid materials, comparable to the diffusion rate of liquid water molecules at room temperature. The diffusion rate is determined by an intricate combination of quantum effects and dynamic interplay with the displacement of host atoms that is still only partially understood. Here we present direct observations of the spatial and temporal changes in the diffusion-induced concentration profiles in a vanadium single crystal and we show that the results represent the experimental counterpart of the full time and spatial solution of Fick's diffusion equation. We validate the approach by determining the diffusion rate of hydrogen in a single crystal vanadium (001) film, with net diffusion in the [110] direction. PMID:22692535

Using light transmission to watch hydrogen diffuse

NASA Astrophysics Data System (ADS)

Pálsson, Gunnar K.; Bliersbach, Andreas; Wolff, Max; Zamani, Atieh; Hjörvarsson, Björgvin

2012-06-01

Because of its light weight and small size, hydrogen exhibits one of the fastest diffusion rates in solid materials, comparable to the diffusion rate of liquid water molecules at room temperature. The diffusion rate is determined by an intricate combination of quantum effects and dynamic interplay with the displacement of host atoms that is still only partially understood. Here we present direct observations of the spatial and temporal changes in the diffusion-induced concentration profiles in a vanadium single crystal and we show that the results represent the experimental counterpart of the full time and spatial solution of Fick's diffusion equation. We validate the approach by determining the diffusion rate of hydrogen in a single crystal vanadium (001) film, with net diffusion in the [110] direction.

Simplified models of rates of CO2 mineralization in Geologic Carbon Storage

NASA Astrophysics Data System (ADS)

DePaolo, D. J.; Zhang, S.

2017-12-01

Geologic carbon storage (GCS) reverses the flow of carbon to the atmosphere, returning the carbon to long-term geologic storage. Models suggest that most of the injected CO2 will be "trapped" in the subsurface by physical means, but the most risk-free and permanent form of carbon storage is as carbonate minerals (Ca,Mg,Fe)CO3. The transformation of CO2 to carbonate minerals requires supply of divalent cations by dissolution of silicate minerals. Available data suggest that rates of transformation are difficult to predict. We show that the chemical kinetic observations and experimental results, when reduced to a single timescale that describes the fractional rate at which cations are released to solution by mineral dissolution, show sufficiently systematic behavior that the rates of mineralization can be estimated with reasonable certainty. Rate of mineralization depends on both the abundance (determined by the reservoir rock mineralogy) and the rate at which cations are released by dissolution into pore fluid that has been acidified with dissolved CO2. Laboratory-measured rates and field observations give values spanning 8 to 10 orders of magnitude, but when evaluated in the context of reservoir-scale reactive transport simulations, this range becomes much smaller. Reservoir scale simulations indicate that silicate mineral dissolution and subsequent carbonate mineral precipitation occur at pH 4.5 to 6, fluid flow velocity less than 5m/yr, and 50-100 years or more after the start of injection. These constraints lead to estimates of 200 to 2000 years for conversion of 60-90% of injected CO2 when the reservoir rock has a sufficient volume fraction of divalent cation-bearing silicate minerals (ca. 20%), and confirms that when reservoir rock mineralogy is not favorable the fraction of CO2 converted to carbonate minerals is minimal over 104 years. A sufficient amount of reactive minerals represents the condition by which the available cations per volume of rock plus pore space exceeds the locally trapped CO2 by a factor of two or more. Our approach may allow for rapid evaluation of mineralization potential of subsurface storage reservoirs, and illustrates how reservoir scale modeling can be integrated with other observations to address key issues for engineering geologic systems.

Biosorption of copper ions from dilute aqueous solutions on base treated rubber (Hevea brasiliensis) leaves powder: kinetics, isotherm, and biosorption mechanisms.

PubMed

Wan Ngah, W S; Hanafiah, M A K M

2008-01-01

The efficiency of sodium hydroxide treated rubber (Hevea brasiliensis) leaves powder (NHBL) for removing copper ions from aqueous solutions has been investigated. The effects of physicochemical parameters on biosorption capacities such as stirring speed, pH, biosorbent dose, initial concentrations of copper, and ionic strength were studied. The biosorption capacities of NHBL increased with increase in pH, stirring speed and copper concentration but decreased with increase in biosorbent dose and ionic strength. The isotherm study indicated that NHBL fitted well with Langmuir model compared to Freundlich and Dubinin-Radushkevich models. The maximum biosorption capacity determined from Langmuir isotherm was 14.97 mg/g at 27 degrees C. The kinetic study revealed that pseudosecond order model fitted well the kinetic data, while Boyd kinetic model indicated that film diffusion was the main rate determining step in biosorption process. Based on surface area analysis, NHBL has low surface area and categorized as macroporous. Fourier transform infrared (FT-IR) analyses revealed that hydroxyl, carboxyl, and amino are the main functional groups involved in the binding of copper ions. Complexation was one of the main mechanisms for the removal of copper ions as indicated by FT-IR spectra. Ion exchange was another possible mechanism since the ratio of adsorbed cations (Cu2+ and H+) to the released cations (Na+, Ca2+, and Mg2+) from NHBL was almost unity. Copper ions bound on NHBL were able to be desorbed at > 99% using 0.05 mol/L HCl, 0.01 mol/L HNO3, and 0.01 mol/L EDTA solutions.

Selective Capture of Cesium and Thallium from Natural Waters and Simulated Wastes with Copper Ferrocyanide Functionalized Mesoporous Silica

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

Sangvanich, Thanapon; Sukwarotwat, Vichaya; Wiacek, Robert J.

2010-10-15

Copper(II) ferrocyanide immobilized inside mesoporous silica MCM-41 supports (Cu-FC-EDA-SAMMSTM) has been evaluated against iron(III) hexacyanoferrate(II) (insoluble Prussian blue) for the sorption of cesium (Cs+) and thallium (Tl+) from natural waters and simulated wastes. The affinities (in term of distribution coefficients, Kd) of both sorbents for Cs and Tl were measured as a function of solution pH, competing cations, and matrices. For the entire pH studied (pH 0.1 to 7.3), Cu-FC-EDA-SAMMS had higher affinities for Cs and Tl (one to two orders of magnitude higher Kd) than Prussian blue and was less negatively impacted by the solution pH, competing cations, andmore » matrices. The adsorption isotherms and kinetics of the two sorbents for Cs and/or Tl were also determined in seawater and simulated acid and alkaline wastes. SAMMS outperformed Prussian blue in terms of maximum adsorption capacity (e.g., 21.7 versus 2.6 mg Cs/g in acid waste stimulant, pH 1.1), and rate (e.g., over 95 wt% of Cs was removed after 2 minutes with SAMMS, while only 75 wt% was removed with Prussian blue). The lower affinity, capacity, and rate of Cs and Tl sorption on Prussian blue than those on Cu-FC-EDA-SAMMS were attributed to the molecular pore sizes, which restrict mass transport, and the insoluble Cs abducts of the Prussian blue, which restrict the ability of neighboring binding sites to further bind Cs ions. On the other hand, the large pores of SAMMS not only enable faster diffusion and faster binding chemistry, but they also allow isolation of binding sites so that one Cs binding event does not impact further Cs binding. In addition, iron (Fe) dissolved from insoluble Prussian blue over 10-fold of that from Cu-FC-EDA-SAMMS after 24 hours of contact time, indicating poorer material stability of Prussian blue.« less

Redistribution kinetics of Ga and Al substitutions in yttrium iron garnet

NASA Astrophysics Data System (ADS)

Röschmann, P.

1980-01-01

Results are presented for the octahedral-tetrahedral site redistribution rate of Ga or Al and Fe in YIG in the temperature range 773 to 1523 K. The activation energy for the cation transfer decreases with increasing the oxygen vacancy concentration by annealing. A screening model describes qualitatively the effects of enhanced cation redistribution.

Automation of flow injection gas diffusion-ion chromatography for the nanomolar determination of methylamines and ammonia in seawater and atmospheric samples

PubMed Central

Gibb, Stuart W.; Wood, John W.; Fauzi, R.; Mantoura, C.

1995-01-01

The automation and improved design and performance of Flow Injection Gas Diffusion-Ion Chromatography (FIGD-IC), a novel technique for the simultaneous analysis of trace ammonia (NH3) and methylamines (MAs) in aqueous media, is presented. Automated Flow Injection Gas Diffusion (FIGD) promotes the selective transmembrane diffusion of MAs and NH3 from aqueous sample under strongly alkaline (pH > 12, NaOH), chelated (EDTA) conditions into a recycled acidic acceptor stream. The acceptor is then injected onto an ion chromatograph where NH3 and the MAs are fully resolved as their cations and detected conductimetrically. A versatile PC interfaced control unit and data capture unit (DCU) are employed in series to direct the selonoid valve switching sequence, IC operation and collection of data. Automation, together with other modifications improved both linearily (R2 > 0.99 MAs 0-100 nM, NH3 0-1000 nM) and precision (<8%) of FIGD-IC at nanomolar concentrations, compared with the manual procedure. The system was successfully applied to the determination of MAs and NH3 in seawater and in trapped particulate and gaseous atmospheric samples during an oceanographic research cruise. PMID:18925047

Effect of Extra-Framework Cations of LTL Nanozeolites to Inhibit Oil Oxidation

NASA Astrophysics Data System (ADS)

Tan, Kok-Hou; Cham, Hooi-Ying; Awala, Hussein; Ling, Tau Chuan; Mukti, Rino R.; Wong, Ka-Lun; Mintova, Svetlana; Ng, Eng-Poh

2015-06-01

Lubricant oils take significant part in current health and environmental considerations since they are an integral and indispensable component of modern technology. Antioxidants are probably the most important additives used in oils because oxidative deterioration plays a major role in oil degradation. Zeolite nanoparticles (NPs) have been proven as another option as green antioxidants in oil formulation. The anti-oxidative behavior of zeolite NPs is obvious; however, the phenomenon is still under investigation. Herein, a study of the effect of extra-framework cations stabilized on Linde Type L (LTL) zeolite NPs (ca. 20 nm) on inhibition of oxidation in palm oil-based lubricant oil is reported. Hydrophilic LTL zeolites with a Si/Al ratio of 3.2 containing four different inorganic cations (Li+, Na+, K+, Ca2+) were applied. The oxidation of the lubricant oil was followed by visual observation, colorimetry, fourier transform infrared (FTIR) spectroscopy, 1H NMR spectroscopy, total acid number (TAN), and rheology analyses. The effect of extra-framework cations to slow down the rate of oil oxidation and to control the viscosity of oil is demonstrated. The degradation rate of the lubricant oil samples is decreased considerably as the polarizability of cation is increased with the presence of zeolite NPs. More importantly, the microporous zeolite NPs have a great influence in halting the steps that lead to the polymerization of the oils and thus increasing the lifetime of oils.

Molecular dynamics in stiff ionene below glass transition.

PubMed

Makrocka-Rydzyk, M; Glowinkowski, S; Jurga, S; Meyer, W H

1995-08-01

Temperature dependences of proton and fluorine second moments and spin-lattice relaxation time T1 below glass transition were measured in glassy "I-Do,Pip-Me-BF4" ionene. The existence of motions of methyl groups and segments linking the cationic centers, namely piperidinium rings and trimethylene groups, for the polymeric part of ionene were established. Isotropic rotation of the counter-ion was evidenced and its limited diffusion suggested. To interpret the proton and fluorine relaxation data, a Davidson-Cole distribution of correlation times was assumed.

Preliminary Evaluations of Polymer-based Lithium Battery Electrolytes Under Development for the Polymer Electrolyte Rechargeable Systems Program

NASA Technical Reports Server (NTRS)

Manzo, Michelle A.; Bennett, William R.

2003-01-01

A component screening facility has been established at The NASA Glenn Research Center (GRC) to evaluate candidate materials for next generation, lithium-based, polymer electrolyte batteries for aerospace applications. Procedures have been implemented to provide standardized measurements of critical electrolyte properties. These include ionic conductivity, electronic resistivity, electrochemical stability window, cation transference number, salt diffusion coefficient and lithium plating efficiency. Preliminary results for poly(ethy1ene oxide)-based polymer electrolyte and commercial liquid electrolyte are presented.

Polymers in separation processes

NASA Astrophysics Data System (ADS)

Wieszczycka, Karolina; Staszak, Katarzyna

2017-05-01

Application of polymer materials as membranes and ion-exchange resins was presented with a focus on their use for the recovery of metal ions from aqueous solutions. Several membrane techniques were described including reverse osmosis, nanofiltration, ultrafiltration, diffusion and Donnan dialysis, electrodialysis and membrane extraction system (polymer inclusion and supported membranes). Moreover, the examples of using ion-exchange resins in metal recovery were presented. The possibility of modification of the resin was discussed, including hybrid system with metal cation or metal oxide immobilized on polymer matrices or solvent impregnated resin.

Respirometric biomonitor for the control of industrial effluent toxicity

NASA Astrophysics Data System (ADS)

Campanella, Luigi; Favero, G.; Mastrofini, D.; Tomassetti, M.

1995-10-01

A yeast cell biosystem has been recently developed for the total toxicity testing of a sample that may contain a number of different polluting species. The method uses an amperometric gas diffusion oxygen sensor as indicating electrode and is based on the perturbation of the respiratory activity of the immobilized yeast Saccharomyces cerevisiae; glucose acts as substrate. Several toxic substances were tested: metal ions, phenol and cationic, anionic or nonionic surfactants. Some results of a monitoring program of an industrial wastewater are also reported and discussed.

γ-Fe 2 O 3 Nanocrystalline Microspheres with Hybrid Behavior of Battery-Supercapacitor for Superior Lithium Storage

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

Tian, Lei-Lei; Zhang, Ming-Jian; Wu, Chao

Maghemite (γ-Fe2O3) nanocrystalline microspheres (MNMs) self-assembled with 52 nm nanocrystals bridged with FeOOH around grain boundaries were formed by solvothermal reaction and thermal oxidation. The unique architecture endows the MNMs with the lithium storage behavior of a hybrid battery-supercapacitor electrode: initial charge capacity of 1060 mAh g–1 at the 100 mA g–1 rate, stable cyclic capacity of 1077.9 mAh g–1 at the same rate after 140 cycles, and rate capability of 538.8 mAh g–1 at 2400 mA g–1. This outstanding performance was attributed to the nanocrystal superiority, which shortens the Li+ diffusion paths. The mechanism of this hybrid anode materialmore » was investigated with experimental measurements and structural analysis. The results indicate that at the first discharge, the MNM nanocrystal microsphere, whose structure can buffer the volume change that occurs during lithiation/delithiation, goes through four stages: Li+ insertion in cation vacancies, spinel-to-rocksalt transformation, Li+ intercalation of Li1.75+xFe2O3 nanocrystals, and interfacial Li storage around nanocrystal boundaries. Only the latter two stages were reversible at and after the second charging/discharging cycle, exhibiting the hybrid behavior of a battery-supercapacitor with superior lithium storage.« less

Atom Probe Tomography of Phase and Grain Boundaries in Experimentally-Deformed and Hot-Pressed Wehrlite

NASA Astrophysics Data System (ADS)

Cukjati, J.; Parman, S. W.; Cooper, R. F.; Zhao, N.

2017-12-01

Atom probe tomography (APT) was used to characterize the chemistry of three grain boundaries: an olivine-olivine (ol-ol) and olivine-clinopyroxene (ol-cpx) boundary in fine-grained experimentally-deformed wehrlite and an ol-cpx boundary in a fine-grained, hot-pressed wehrlite. Grain boundaries were extracted and formed into APT tips using a focused ion beam (FIB). The tips were analyzed in a reflectron-equipped LEAP4000HR (Harvard University) at 1% or 0.5% detection rate, 5pJ laser energy and 100kHz pulse rate. Total ion counts are between 40 and 100 million per tip. Examination of grain and phase boundaries in wehrlite are of interest since slow-diffusing and olivine-incompatible cations present in cpx (e.g. Ca and Al) may control diffusion-accommodated grain boundary sliding and affect mantle rheology (Sundberg & Cooper, 2008). At steady state, ol-cpx aggregates are weaker than either ol or cpx end member, the results of which are not currently well-explained. We investigate grain boundary widths to understand the transport of olivine-incompatible elements. Widths of grain/phase boundary chemical segregation are between 3nm and 6nm for deformed ol-ol and ol-cpx samples; minimally-deformed (hot-pressed) samples having slightly wider chemical segregation widths. Chemical segregation widths were determined from profiles of Na, Al, P, Cl, K, Ca, or Ni, although not all listed elements can be used for all samples (e.g. Na, K segregation profiles can only be observed for ol-ol sample). These estimates are consistent with prior estimates of grain boundary segregation by atom probe tomography on ol-ol and opx-opx samples (Bachhav et al., 2015) and are less than ol-ol interface widths analyzed by STEM/EDX (Hiraga, Anderson, & Kohlstedt, 2007). STEM/EDX will be performed on deformed wehrlite to investigate chemical profile as a function of applied stress orientation and at length scales between those observable by APT and EPMA. Determination of phase boundary chemistry and structure allows for better modeling of the rheology of multiphase aggregates and better understanding of diffusive transport and storage of incompatible elements along grain boundaries.

Sustained release of hepatocyte growth factor by cationic self-assembling peptide/heparin hybrid hydrogel improves β-cell survival and function through modulating inflammatory response

PubMed Central

Liu, Shuyun; Zhang, Lanlan; Cheng, Jingqiu; Lu, Yanrong; Liu, Jingping

2016-01-01

Inflammatory response is a major cause of grafts dysfunction in islet transplantation. Hepatocyte growth factor (HGF) had shown anti-inflammatory activity in multiple diseases. In this study, we aim to deliver HGF by self-assembling peptide/heparin (SAP/Hep) hybrid gel to protect β-cell from inflammatory injury. The morphological and slow release properties of SAPs were analyzed. Rat INS-1 β-cell line was treated with tumor necrosis factor α in vitro and transplanted into rat kidney capsule in vivo, and the viability, apoptosis, function, and inflammation of β-cells were evaluated. Cationic KLD1R and KLD2R self-assembled to nanofiber hydrogel, which showed higher binding affinity for Hep and HGF because of electrostatic interaction. Slow release of HGF from cationic SAP/Hep gel is a two-step mechanism involving binding affinity with Hep and molecular diffusion. In vitro and in vivo results showed that HGF-loaded KLD2R/Hep gel promoted β-cell survival and insulin secretion, and inhibited cell apoptosis, cytokine release, T-cell infiltration, and activation of NFκB/p38 MAPK pathways in β-cells. This study suggested that SAP/Hep gel is a promising carrier for local delivery of bioactive proteins in islet transplantation. PMID:27729786

Interfacial Redox Reactions Associated Ionic Transport in Oxide-Based Memories.

PubMed

Younis, Adnan; Chu, Dewei; Shah, Abdul Hadi; Du, Haiwei; Li, Sean

2017-01-18

As an alternative to transistor-based flash memories, redox reactions mediated resistive switches are considered as the most promising next-generation nonvolatile memories that combine the advantages of a simple metal/solid electrolyte (insulator)/metal structure, high scalability, low power consumption, and fast processing. For cation-based memories, the unavailability of in-built mobile cations in many solid electrolytes/insulators (e.g., Ta 2 O 5 , SiO 2 , etc.) instigates the essential role of absorbed water in films to keep electroneutrality for redox reactions at counter electrodes. Herein, we demonstrate electrochemical characteristics (oxidation/reduction reactions) of active electrodes (Ag and Cu) at the electrode/electrolyte interface and their subsequent ions transportation in Fe 3 O 4 film by means of cyclic voltammetry measurements. By posing positive potentials on Ag/Cu active electrodes, Ag preferentially oxidized to Ag + , while Cu prefers to oxidize into Cu 2+ first, followed by Cu/Cu + oxidation. By sweeping the reverse potential, the oxidized ions can be subsequently reduced at the counter electrode. The results presented here provide a detailed understanding of the resistive switching phenomenon in Fe 3 O 4 -based memory cells. The results were further discussed on the basis of electrochemically assisted cations diffusions in the presence of absorbed surface water molecules in the film.

Effects of variation in chain length on ternary polymer electrolyte - Ionic liquid mixture - A molecular dynamics simulation study

NASA Astrophysics Data System (ADS)

Raju, S. G.; Hariharan, Krishnan S.; Park, Da-Hye; Kang, HyoRang; Kolake, Subramanya Mayya

2015-10-01

Molecular dynamics (MD) simulations of ternary polymer electrolyte - ionic liquid mixtures are conducted using an all-atom model. N-alkyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([CnMPy][TFSI], n = 1, 3, 6, 9) and polyethylene oxide (PEO) are used. Microscopic structure, energetics and dynamics of ionic liquid (IL) in these ternary mixtures are studied. Properties of these four pure IL are also calculated and compared to that in ternary mixtures. Interaction between pyrrolidinium cation and TFSI is stronger and there is larger propensity of ion-pair formation in ternary mixtures. Unlike the case in imidazolium IL, near neighbor structural correlation between TFSI reduces with increase in chain length on cation in both pure IL and ternary mixtures. Using spatial density maps, regions where PEO and TFSI interact with pyrrolidinium cation are identified. Oxygens of PEO are above and below the pyrrolidinium ring and away from the bulky alkyl groups whereas TFSI is present close to nitrogen atom of CnMPy. In pure IL, diffusion coefficient (D) of C3MPy is larger than of TFSI but D of C9MPy and C6MPy are larger than that of TFSI. The reasons for alkyl chain dependent phenomena are explored.

The experimental study of matching between centrifugal compressor impeller and diffuser

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

Tamaki, H.; Nakao, H.; Saito, M.

1999-01-01

the centrifugal compressor for a marine use turbocharger with its design pressure ratio of 3.2 was tested with a vaneless diffuser and various vaned diffusers. Vaned diffusers were chosen to cover impeller operating range as broad as possible. The analysis of the static pressure ratio in the impeller and the diffusing system, consisting of the diffuser and scroll, showed that there were four possible combinations of characteristics of impeller pressure ratio and diffusing system pressure ratio. The flow rate, Q{sub P}, where the impeller achieved maximum static pressure ratio, was surge flow rate of the centrifugal compressor determined by themore » critical flow rate. In order to operate the compressor at a rate lower than Q{sub P}, the diffusing system, whose pressure recovery factor was steep negative slope near Q{sub P}, was needed. When the diffuser throat area was less than a certain value, the compressor efficiency deteriorated; however, the compressor stage pressure ratio was almost constant. In this study, by reducing the diffuser throat area, the compressor could be operated at a flow rate less than 40% of its design flow rate. Analysis of the pressure ratio in the impeller and diffusing systems at design and off-design speeds showed that the irregularities in surge line occurred when the component that controlled the negative slope on the compressor stage pressure ratio changed.« less

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

NASA Technical Reports Server (NTRS)

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

1993-01-01

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

The importance of atmospheric base cation deposition for preventing soil acidification in the Athabasca Oil Sands Region of Canada

Treesearch

Shaun A. Watmough; Colin J. Whitfield; Mark E. Fenn

2014-01-01

Industrial activities in the oil sands region of Alberta, Canada have resulted in greatly elevated emissions of SO2 and N (NOx and NH3) and there are concerns over possible widespread ecosystem acidification. Acid sensitive soils in the region are common and have very low base cation weathering rates...

Partial cordierite breakdown during post-seismic recovery: the significance of plastic deformation for cation diffusion and metamorphic equilibrium

NASA Astrophysics Data System (ADS)

Büttner, Steffen; Costin, Gelu

2010-05-01

Brittle intra-crystal fracturing occurred during a microseismic event in migmatites of the Ordovician Sierras Pampeanas (NW Argentina), forming micro-shear zones and brittle fragments in cordierite. The seismic event occurred at amphibolite facies P-T conditions under high strain rates (≥ 10-7 s-1). During post-seismic recovery and coarsening of crystal fragments, primary cordierite (XMg=0.65) underwent partial breakdown along the deformation zone, forming a secondary mineral assemblage in an alteration zone along grain boundaries of coarsened crystal fragments. The secondary assemblage is restricted to the recovery zone. The breakdown of primary cordierite (CrdP) is accompanied by the formation of secondary sillimanite, magnetite, staurolite (XMg=0.24, ~0.5 wt% ZnO), quartz, and secondary cordierite (CrdS; XMg=0.70-0.80). CrdS, volumetrically the most important secondary phase, forms by diffusion of Mg and Fe, altering CrdP by Fe loss and uptake of Mg. All other secondary phases form by nucleation. Two simultaneous cordierite breakdown reactions have been balanced using CSpace 1.01: 100 CrdP (XMg 0.65) = 21.8 Sil +12.8 Mag + 33.5 Qtz + 5.6 H2O + 89.1 CrdS (XMg 0.75) 100 CrdP (XMg0.65) = 8.1 Mag + 53.6 Qtz + 4.5 H2O + 8.1 St (XMg0.24) + 83.3 CrdS (XMg 0.75) The bulk chemical major element composition of the alteration zone is nearly identical to the composition of primary cordierite, suggesting that elemental exchange between the alteration zone and the cordierite matrix is limited. However, minor fluid influx, supplying Zn, K, Si, and O is indicated by the composition of staurolite, minor formation of biotite and quartz, and by the oxidation of Fe2+ within the alteration zone. The modal composition of the alteration zone has been determined by point counting, which yields similar results like CSpace results (converted into vol%), and MODAN calculations, which calculates modes based on the average alteration zone composition, and the compositions of secondary phases. The average modal composition of the alteration zone is: 2.3 Sil + 2.0 Mag + 4.3 Qtz + 3.9 St+ 87.5 CrdS (vol%) Thermodynamic modelling of primary cordierite breakdown using Theriak Domino shows that the observed breakdown is possible only in a small P -T window around P =450 MPa and T =555 ° C, which is in good agreement with the retrograde P - T path of the Sierra de Quilmes migmatites. Modes calculated using Theriak Domino are similar to results using descriptive methods (point counting), or methods based on chemistry and petrography (MODAN, CSpace). Since modes predicted on the assumption of petrological equilibrium are close to the observed modes, the breakdown reaction seen in the alteration zone most likely represents conditions of, or close to, thermodynamic equilibrium. The formation of the secondary mineral assemblage in the alteration zone depends upon the efficient supply of cations, essentially Si, Al, Fe and Mg. The bulk composition of new secondary minerals (Qtz, St, Mag, Sil) is enriched in Fe compared to CrdP, whereas CrdS is Fe depleted. The provision of Si and Al required for Sil, Qtz, and St can be assigned to partial cordierite breakdown. The excess Fe needed for Mag and St, and the removal of surplus Mg from CrdP breakdown, depends on Fe-Mg diffusion within CrdS. Since CrdS forms exclusively in the post-seismic recovery zone, we interpret dislocation creep, and hence cation diffusion related to plastic deformation, as the key process for the formation of reaction products reflecting thermodynamic equilibrium.

Overall adsorption rate of metronidazole, dimetridazole and diatrizoate on activated carbons prepared from coffee residues and almond shells.

PubMed

Flores-Cano, J V; Sánchez-Polo, M; Messoud, J; Velo-Gala, I; Ocampo-Pérez, R; Rivera-Utrilla, J

2016-03-15

This study analyzed the overall adsorption rate of metronidazole, dimetridazole, and diatrizoate on activated carbons prepared from coffee residues and almond shells. It was also elucidated whether the overall adsorption rate was controlled by reaction on the adsorbent surface or by intraparticle diffusion. Experimental data of the pollutant concentration decay curves as a function of contact time were interpreted by kinetics (first- and second-order) and diffusion models, considering external mass transfer, surface and/or pore volume diffusion, and adsorption on an active site. The experimental data were better interpreted by a first-order than second-order kinetic model, and the first-order adsorption rate constant varied linearly with respect to the surface area and total pore volume of the adsorbents. According to the diffusion model, the overall adsorption rate is governed by intraparticle diffusion, and surface diffusion is the main mechanism controlling the intraparticle diffusion, representing >90% of total intraparticle diffusion. Copyright © 2015 Elsevier Ltd. All rights reserved.

Rates of CO2 Mineralization in Geological Carbon Storage.

PubMed

Zhang, Shuo; DePaolo, Donald J

2017-09-19

Geologic carbon storage (GCS) involves capture and purification of CO 2 at industrial emission sources, compression into a supercritical state, and subsequent injection into geologic formations. This process reverses the flow of carbon to the atmosphere with the intention of returning the carbon to long-term geologic storage. Models suggest that most of the injected CO 2 will be "trapped" in the subsurface by physical means, but the most risk-free and permanent form of carbon storage is as carbonate minerals (Ca,Mg,Fe)CO 3 . The transformation of CO 2 to carbonate minerals requires supply of the necessary divalent cations by dissolution of silicate minerals. Available data suggest that rates of transformation are highly uncertain and difficult to predict by standard approaches. Here we show that the chemical kinetic observations and experimental results, when they can be reduced to a single cation-release time scale that describes the fractional rate at which cations are released to solution by mineral dissolution, show sufficiently systematic behavior as a function of pH, fluid flow rate, and time that the rates of mineralization can be estimated with reasonable certainty. The rate of mineralization depends on both the abundance (determined by the reservoir rock mineralogy) and the rate at which cations are released from silicate minerals by dissolution into pore fluid that has been acidified with dissolved CO 2 . Laboratory-measured rates and field observations give values spanning 8 to 10 orders of magnitude, but when they are evaluated in the context of a reservoir-scale reactive transport simulation, this range becomes much smaller. The reservoir scale simulations provide limits on the applicable conditions under which silicate mineral dissolution and subsequent carbonate mineral precipitation are likely to occur (pH 4.5 to 6, fluid flow velocity less than 5 m/year, and 50-100 years or more after the start of injection). These constraints lead to estimates of 200 to 2000 years for conversion of 60-90% of injected CO 2 when the reservoir rock has a sufficient volume fraction of divalent cation-bearing silicate minerals and confirms that when reservoir rock mineralogy is not favorable the fraction of CO 2 converted to carbonate minerals is minimal over 10 4 years. A sufficient amount of reactive minerals is typically about 20% by volume. Our approach may allow for rapid evaluation of mineralization potential of subsurface storage reservoirs and illustrates how reservoir scale modeling can be integrated with other observations to address key issues relating to engineering of geologic systems.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Modeling of Diffusion Based Correlations Between Heart Rate Modulations and Respiration Pattern

DTIC Science & Technology

2001-10-25

1 of 4 MODELING OF DIFFUSION BASED CORRELATIONS BETWEEN HEART RATE MODULATIONS AND RESPIRATION PATTERN R.Langer,(1) Y.Smorzik,(2) S.Akselrod,(1...generations of the bronchial tree. The second stage describes the oxygen diffusion process from the pulmonary gas in the alveoli into the pulmonary...patterns (FRC, TV, rate). Keywords – Modeling, Diffusion , Heart Rate fluctuations I. INTRODUCTION Under a whole-body management perception, the

Singlet and doublet states UV-vis spectrum and electronic properties of 3-methylchrysene and 4-methylchrysene in glass matrix.

PubMed

Husain, Mudassir M; Tandon, H C; Varadwaj, Pradeep R

2008-03-01

The ultraviolet-visual spectrum of 3-methylchrysene, 4-methylchrysene and their radical cations formed by ultraviolet radiations, were measured in glass matrix at the room temperature. In the measured singlet state spectrum we were able to identify the alpha, p, beta, beta' (Clar's) or (1)L(b), (1)L(a)(1)B(b), (1)B(a) (Platt's notation) bands. The presence of alpha, beta or (1)L(b), (1)B(b) was confirmed by calculating their wavelength ratio lambda(alpha)/lambda(beta). Since matrix induces perturbation in the measured spectrum; it becomes necessary to take into account the perturbation while computing the spectrum. An effort has been made in this work to simulate the electronic spectrum in the same environment as is measured. This study presents the first calculated spectrum of these systems and their cations in glass matrix by semi empirical methods. To observe the magnitude of perturbation and hence to see the spectral shift in glass matrix, the spectrum was calculated in the free state as well. Spectral properties such as frontier orbitals gap, dipole moment, mean polarizabilities and its tensors were also computed both in glass matrix and free state using semiemperical method. The measured bands of 3-methylchrysene cation at wavelength 416.50 and 473.85 nm closely match with the available diffuse intersteallar bands (DIBs) at 417.55 and 472.64 nm, respectively. Also the observed 474.85 nm band of 4-methylchrysene cation matches the DIB at 476.00 nm.

Experimental Electronic Spectroscopy of Two PAHs: Naphthalene and 2-METHYL Naphthalene

NASA Astrophysics Data System (ADS)

Friha, H.; Feraud, G.; Pino, T.; Brechignac, Ph.; Parneix, P.; Dhaoudi, Z.; Jaidane, N.; Galila, H.; Troy, T.; Schmidt, T.

2011-06-01

The presence of polycyclic aromatic hydrocarbons (PAHs) in the interstellar medium (ISM) was suggested in the mid-80's. Since then, their important role in the physico-chemical evolution of the ISM has been confirmed. Interstellar PAHs have been in particular proposed as possible carriers of some Diffuse Interstellar Bands (DIBs). These absorption bands are seen in the spectra of reddened stars from the visible to the near infrared and constitute a major astrophysical issue. Our purpose is to obtain electronic spectra of gas phase PAHs which will be used to probe their participation to the interstellar extinction curve from the visible (DIBs) to the UV (bump). For this goal PAHs cations represent an excellent set of target species. A new way of forming PAH+-Ar_n clusters cations has been implemented in the experimental set-up 'ICARE' at ISMO (Orsay) giving us the capability to measure the electronic spectra of cold PAH cations in the gas phase through the "Ar tagging" trick. Two molecules have been investigated in this way: naphthalene (C_1_0H_8) and 2- methyl naphthalene (C_1_1H_1_0). Clusters of naphthalene and (or 2-methyl-naphthalene) with Ar atoms are first formed in a supersonic jet, before being hit by a 281 nm laser beam which photo-ionizes the clusters which are then injected in a molecular beam through a skimmer. A tunable laser beam crossing downstream photo-dissociates the cations. The bare PAH fragments are detected using a Time-Of-Flight spectrometer while scanning the visible laser wavelength from 470 to 690 nm.

Molecules in motion: influences of diffusion on metabolic structure and function in skeletal muscle.

PubMed

Kinsey, Stephen T; Locke, Bruce R; Dillaman, Richard M

2011-01-15

Metabolic processes are often represented as a group of metabolites that interact through enzymatic reactions, thus forming a network of linked biochemical pathways. Implicit in this view is that diffusion of metabolites to and from enzymes is very fast compared with reaction rates, and metabolic fluxes are therefore almost exclusively dictated by catalytic properties. However, diffusion may exert greater control over the rates of reactions through: (1) an increase in reaction rates; (2) an increase in diffusion distances; or (3) a decrease in the relevant diffusion coefficients. It is therefore not surprising that skeletal muscle fibers have long been the focus of reaction-diffusion analyses because they have high and variable rates of ATP turnover, long diffusion distances, and hindered metabolite diffusion due to an abundance of intracellular barriers. Examination of the diversity of skeletal muscle fiber designs found in animals provides insights into the role that diffusion plays in governing both rates of metabolic fluxes and cellular organization. Experimental measurements of metabolic fluxes, diffusion distances and diffusion coefficients, coupled with reaction-diffusion mathematical models in a range of muscle types has started to reveal some general principles guiding muscle structure and metabolic function. Foremost among these is that metabolic processes in muscles do, in fact, appear to be largely reaction controlled and are not greatly limited by diffusion. However, the influence of diffusion is apparent in patterns of fiber growth and metabolic organization that appear to result from selective pressure to maintain reaction control of metabolism in muscle.

Impact of wine production on the fractionation of copper and iron in Chardonnay wine: Implications for oxygen consumption.

PubMed

Rousseva, Michaela; Kontoudakis, Nikolaos; Schmidtke, Leigh M; Scollary, Geoffrey R; Clark, Andrew C

2016-07-15

Copper and iron in wine can influence oxidative, reductive and colloidal stability. The current study utilises a solid phase extraction technique to fractionate these metals into hydrophobic, cationic and residual forms, with quantification by ICP-OES. The impact of aspects of wine production on the metal fractions was examined, along with the relationship between metal fractions and oxygen decay rates. Addition of copper and iron to juice, followed by fermentation, favoured an increase in all of their respective metal fractions in the wine, with the largest increase observed for the cationic form of iron. Bentonite fining of the protein-containing wines led to a significant reduction in the cationic fraction of copper and an increase in the cationic form of iron. Total copper correlated more closely with oxygen consumption in the wine compared to total iron, and the residual and cationic forms of copper provided the largest contribution to this impact. Copyright © 2016 Elsevier Ltd. All rights reserved.

Diffusion in Brain Extracellular Space

PubMed Central

Syková, Eva; Nicholson, Charles

2009-01-01

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

The photodynamic response of two rodent tumour models to four zinc (II)-substituted phthalocyanines.

PubMed Central

Cruse-Sawyer, J. E.; Griffiths, J.; Dixon, B.; Brown, S. B.

1998-01-01

Four novel zinc (II)-substituted phthalocyanines, varying in charge and hydrophobicity, were evaluated in vivo as new photosensitizers for photodynamic therapy. Two rat tumours with differing vascularity were used: a mammary carcinoma (LMC1) and a fibrosarcoma (LSBD1), with vascular components six times higher in the latter (10.8%+/-1.5) than in the former (1.8%+/-1.4). Each sensitizer was assessed for tumour response relative to normal tissue damage, and optimum doses were selected for further study, ranging from 0.5 to 20 mg kg(-1). Interstitial illumination of the tumours was carried out using a 200-microm-core optical fibre with a 0.5 cm length of diffusing tip, at either 680 or 692 nm, depending on the sensitizer. Light doses of between 200 and 600 J were delivered at a rate of 100 mW from the 0.5-cm diffusing section of the fibre. Maximum mean growth delays ranged from 9 to 13.5 days depending on sensitizer and type of tumour, with the most potent photosensitizer appearing to be the cationic compound. Histopathological changes were investigated after treatment to determine the mechanism by which tumour necrosis was effected. The tumours had the appearance of an infarct and, under the conditions used, the observed damage was shown to be mainly due to ischaemic processes, although some direct tumour cell damage could not be ruled out. Images Figure 4 Figure 5 PMID:9528842

An intrinsically fluorescent dendrimer as a nanoprobe of cell transport.

PubMed

Al-Jamal, Khuloud T; Ruenraroengsak, Pakatip; Hartell, Nicholas; Florence, Alexander T

2006-07-01

Dendrimers, spherical or quasi-spherical synthetic polymers in the nano-size range, have found useful applications as prospective carriers in drug and gene delivery. The investigation of dendrimer uptake by cells has been previously achieved by the incorporation of a fluorescent dye to the dendrimer either by chemical conjugation or by physical interaction. Here we describe the synthesis of two intrinsically fluorescent lysine based cationic dendrimers which lack a fluorophore, but which has sufficient fluorescence intensity to be detected at low concentrations. The nomenclature used to describe our compounds results in, for example the 6th generation dendrimer being notated as Gly-Lys(63) (NH2)(64); Gly denotes that the compound has a glycine in the core coupled to 63 lysine branching units (Lys(63)) and that the surface has 64 free amino groups (NH2)(64). The use of these dendrimers in probing transport avoids the need for fluorescent tagging with its attendant problems. The uptake of Gly-Lys(63) (NH2)(64) into Caco-2 cells was followed using confocal microscopy. Being cationic, it first adsorbs to the cell surface, enters the cytoplasm and reaches the nucleus within 35-45 min. Estimates of the diffusion coefficient of the dendrimer within the cell cytoplasm leads to a value of 6.27 ( +/- 0.49) x 10(-11) cm(2) s(-1), which is up to 1000 times lower than the diffusion coefficient of the dendrimer in water. Intrinsically fluorescent dendrimers of different size and charge are useful probes of transport in cells.

Oxidation of a Commercial Nickel-Based Superalloy under Static Loading

NASA Astrophysics Data System (ADS)

Foss, B. J.; Hardy, M. C.; Child, D. J.; McPhail, D. S.; Shollock, B. A.

2014-12-01

The current demands of the aviation industry for increased gas-turbine efficiency necessitate higher turbine entry temperatures, requiring that alloys exhibit superior oxidation resistance. The synergistic effects of oxidation and mechanical stresses pose a complex issue. The purpose of the current research was to examine the effects of stress on the oxidation and oxygen transport in a commercial nickel-based superalloy. Fine grain RR1000 in both polished and shot-peened conditions was studied for classic (zero load) and statically loaded conditions using integrated two-stage isotopic tracing combined with focused-ion-beam secondary ion mass spectrometry (FIB-SIMS). Cr2O3 external oxide formed with semicontinuous TiO2 above and below. Preferential grain boundary Al2O3 internal oxide formation, γ'-dissolution, and recrystallization occurred subsurface. Oxidation mechanisms were dominated by anionic/cationic growth in the external oxide with inward oxygen transport, initially through the partially unprotective external oxide, then along internal oxide/alloy interfaces. Loading did not influence the oxidation products formed but did bring about expedited oxidation kinetics and changes to the oxide morphology. The oxygen diffusivity D {O/ * } (×10-13 cm2s-1) ranged from 0.39 for the polished alloy to 3.7 for the shot-peened condition under compressive stress. Arguably, the most significant effects took place in the subsurface regions. Increased oxidation kinetics were attributed to the development of fast cation diffusion paths as the alloy deformed by creep.

Interfacial water on crystalline silica: a comparative molecular dynamics simulation study

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

Ho, Tuan A.; Argyris, Dimitrios; Papavassiliou, Dimitrios V.

2011-03-03

All-atom molecular dynamics simulations were conducted to study the dynamics of aqueous electrolyte solutions confined in slit-shaped silica nanopores of various degrees of protonation. Five degrees of protonation were prepared by randomly removing surface hydrogen atoms from fully protonated crystalline silica surfaces. Aqueous electrolyte solutions containing NaCl or CsCl salt were simulated at ambient conditions. In all cases, the ionic concentration was 1 M. The results were quantified in terms of atomic density distributions within the pores, and the self-diffusion coefficient along the direction parallel to the pore surface. We found evidence for ion-specific properties that depend on ion surface,more » water ion, and only in some cases ion ion correlations. The degree of protonation strongly affects the structure, distribution, and the dynamic behavior of confined water and electrolytes. Cl ions adsorb on the surface at large degrees of protonation, and their behavior does not depend significantly on the cation type (either Na+ or Cs+ ions are present in the systems considered). The cations show significant ion-specific behavior. Na+ ions occupy different positions within the pore as the degree of protonation changes, while Cs+ ions mainly remain near the pore center at all conditions considered. For a given degree of protonation, the planar self-diffusion coefficient of Cs+ is always greater than that of Na+ ions. The results are useful for better understanding transport under confinement, including brine behavior in the subsurface, with important applications such as environmental remediation.« less

Polycyclic aromatic hydrocarbon ions and the diffuse interstellar bands

NASA Technical Reports Server (NTRS)

Salama, F.; Allamandola, L. J.

1995-01-01

Neutral naphthalene (C10H8), phenanthrene (C14H10), and pyrene (C16H10) absorb strongly in the ultraviolet and may contribute to the extinction curve. High abundances are required to produce detectable structures. The cations of these Polycyclic Aromatic Hydrocarbons (PAHs) absorb in the visible. C10H8(+) has 12 discrete absorption bands which fall between 6800 and 5000 A. The strongest band at 6741 A falls close to the weak 6742 A diffuse interstellar band (DIB). Five other weaker bands also match DIBs. The possibility that C10H8(+) is responsible for some of the DIBs can be tested by searching for new DIBS at 6520, 6151, and 5965 A, other moderately strong naphthalene cation band positions. If C10H8(+) is indeed responsible for the 6742 A feature, it accounts for 0.3% of the cosmic carbon. The spectrum of C16H10(+) is dominated by a strong band at 4435 A in an Ar matrix and 4395 A in a Ne matrix, a position which falls very close to the strongest DIB, that at 4430 A. If C16H10(+), or a closely related pyrene-like ion is indeed responsible for the 4430 A feature, it accounts for 0.2% of the cosmic carbon. We also report an intense, very broad UV-to-visible continuum which is associated with both ions and could explain how PAHs convert interstellar UV and visible radiation into IR.

Neutral and ionized polycyclic aromatic hydrocarbons, diffuse interstellar bands and the ultraviolet extinction curve

NASA Technical Reports Server (NTRS)

Salama, Farid; Allamandola, Louis John

1993-01-01

Neutral naphthalene C10H8, phenanthrene C14H10 and pyrene C16H10 absorb strongly in the ultraviolet region and may contribute to the extinction curve. High abundances are required to produce detectable structures. The cations of these polycyclic aromatic hydrocarbons (PAHs) absorb in the visible C10H8(+) has 13 discrete absorption bands which fall between 6800 and 4500 A. The strongest band at 6741 A falls close to the weak 6742 A diffuse interstellar band (DIB). Five other weaker bands also match DIBs. The possibility that C10H8(+) is responsible for some of the DIBs can be tested by searching for new DIBs at 6520 and 6151 A, other strong naphthalene cation band positions. If C10H8(+) is indeed responsible for the 6742 A feature, it accounts for 0.3% of the cosmic carbon. The spectrum of C16H10(+) is dominated by a strong band at 4435 A in an Ar matrix and 4395 A in Ne, wavelengths which fall very close to the strongest DIB at 4430 A. If C16H10(+) or a closely related pyrene-like ion, is indeed responsible for the 4430 A feature, it accounts for 0.2% of the cosmic carbon. An intense, very broad UV-to-visible continuum is reported which is associated with both ions and could explain how PAHs convert interstellar UV and visible radiation into IR radiation.

Ion migration in crystalline and amorphous HfOX

NASA Astrophysics Data System (ADS)

Schie, Marcel; Müller, Michael P.; Salinga, Martin; Waser, Rainer; De Souza, Roger A.

2017-03-01

The migration of ions in HfOx was investigated by means of large-scale, classical molecular-dynamics simulations over the temperature range 1000 ≤T /K ≤2000 . Amorphous HfOx was studied in both stoichiometric and oxygen-deficient forms (i.e., with x = 2 and x = 1.9875); oxygen-deficient cubic and monoclinic phases were also studied. The mean square displacement of oxygen ions was found to evolve linearly as a function of time for the crystalline phases, as expected, but displayed significant negative deviations from linear behavior for the amorphous phases, that is, the behavior was sub-diffusive. That oxygen-ion migration was observed for the stoichiometric amorphous phase argues strongly against applying the traditional model of vacancy-mediated migration in crystals to amorphous HfO2. In addition, cation migration, whilst not observed for the crystalline phases (as no cation defects were present), was observed for both amorphous phases. In order to obtain activation enthalpies of migration, the residence times of the migrating ions were analyzed. The analysis reveals four activation enthalpies for the two amorphous phases: 0.29 eV, 0.46 eV, and 0.66 eV (values very close to those obtained for the monoclinic structure) plus a higher enthalpy of at least 0.85 eV. In comparison, the cubic phase is characterized by a single value of 0.43 eV. Simple kinetic Monte Carlo simulations suggest that the sub-diffusive behavior arises from nanoscale confinement of the migrating ions.

Composites of cationic nanofibrillated cellulose and layered silicates: water vapor barrier and mechanical properties.

PubMed

Ho, Thao T T; Zimmermann, Tanja; Ohr, Steffen; Caseri, Walter R

2012-09-26

Composites of trimethylammonium-modified nanofibrillated cellulose and layered silicates (TMA-NFC/LS) were prepared by high-shear homogenization followed by pressure filtration and vacuum hot-pressing, which gave rise to particularly homogeneous dispersion of the silicate particles. Thirteen different clays and micas were employed. Water vapor barrier and mechanical properties (tensile strength, E-modulus, strain at break) of the composite films were investigated, considering the effects of layered silicate types and their concentration (in the range of 0 to 85 wt %). Good interactions between TMA-NFC and LS were obtained due to electrostatic attraction between cationic fibrils and anionic silicate layers, and even favored by high-shear homogenization process. Furthermore, oriented TMA-NFC/LS composite structure was achieved. Layered silicates exerted a pronounced influence on the water vapor barrier and mechanical properties; however, there was no common trend reflecting their types. The transport of water molecules through TMA-NFC/LS composites was studied considering both diffusion and adsorption mechanisms. As a result, diffusion pathways were proposed based on two new and one well-known models: the "native network", "covered fiber composite", and "fiber-brick composite" models. Importantly, it was found that the insertion of layered silicate particles did not improve automatically the barrier properties as indicated by the commonly used "fiber-brick composite" model. Mica R120 at a 50 wt % loading in composites with TMA-NFC matrix showed 30-fold improved water vapor permeability and 5-fold higher E-modulus compared to commercially used base paper.

Excited-State Proton Transfer on the Surface of a Therapeutic Protein, Protamine.

PubMed

Awasthi, Ankur A; Singh, Prabhat K

2017-11-16

Proton transfer reactions on biosurfaces play an important role in a myriad of biological processes. Herein, the excited-state proton transfer reaction of 8-hydroxypyrene-1,3,6-trisulfonate (HPTS) has been investigated in the presence of an important therapeutic protein, Protamine (PrS), using ground-state absorption, steady-state, and detailed time-resolved emission measurements. HPTS forms a 1:1 complex with Protamine with a high association constant of 2.6 × 10 4 M -1 . The binding of HPTS with Protamine leads to a significant modulation in the ground-state prototropic equilibrium causing a downward shift of 1.1 unit in the acidity constant (pK a ). In contrast to a large number of reports of slow proton transfer of HPTS on biosurfaces, interestingly, HPTS registers a faster proton transfer event in the presence of Protamine as compared to that of even the bulk aqueous buffer medium. Furthermore, the dimensionality of the proton diffusion process is also significantly reduced on the surface of Protamine that is in contrast to the behavior of HPTS in the bulk aqueous buffer medium, where the proton diffusion process is three-dimensional. The effect of ionic strength on the binding of HPTS toward PrS suggests a predominant role of electrostatic interaction between anionic HPTS and cationic Protamine, which is further supported by molecular docking simulations which predict that the most preferable binding site for HPTS on the surface of Protamine is surrounded by multiple cationic arginine residues.

Investigation of Sorption and Diffusion Mechanisms, and Preliminary Economic Analysis

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

Bhave, Ramesh R.; Jubin, Robert Thomas; Spencer, Barry B.

This report describes the synthesis and evaluation of molecular sieve zeolite membranes to separate and concentrate tritiated water (HTO) from dilute HTO-bearing aqueous streams. Several monovalent and divalent cation exchanged silico alumino phosphate (SAPO-34) molecular sieve zeolite membranes were synthesized on disk supports and characterized with gas and vapor permeation measurements. The pervaporation process performance was evaluated for the separation and concentration of tritiated water. Experiments were performed using tritiated water feed solution containing tritium at the high end of the range (1 mCi/mL) anticipated in a nuclear fuel processing system that includes both acid and water streams recycling. Themore » tritium concentration was about 0.1 ppm. The permeate was recovered under vacuum. The HTO/H2O selectivity and separation factor calculated from the measured tritium concentrations ranged from 0.99 to 1.23, and 0.83-0.98, respectively. Although the membrane performance for HTO separation was lower than expected, several encouraging observations including molecular sieving and high vapor permeance are reported. Additionally, several new approaches are proposed, such as tuning the sorption and diffusion properties offered by small pore LTA zeolite materials, and cation exchanged aluminosilicates with high metal loading. It is hypothesized that substantially improved preferential transport of tritium (HTO) resulting in a more concentrated permeate can be achieved. Preliminary economic analysis for the membrane-based process to concentrate tritiated water is also discussed.« less

Distribution of Gd(III) ions at the graphene oxide/water interface.

PubMed

Amirov, Rustem R; Shayimova, Julia; Dimiev, Ayrat M

2018-10-01

Graphene oxide (GO) have emerged recently as a novel material for sorbing metal cations from aqueous media. However, the literature data on sorption capacity differ by more than one order in magnitude, and the nature of the chemical bonding between GO and metal cations remains unclear. In this work we show that Gd 3+ ions are bound to GO by both coordinate-covalent bonding and electrostatic attraction with prevailing the former. We provide the complete account for the GO sorption toward Gd 3+ as the function of the Gd 3+ /GO ratio and pH of solution. The upper limits of the strong bonding are determined as 0.70 and 0.16 mmol(Gd 3+ )/g(GO) in the neutral and in the intrinsically acidic solutions, respectively. At large excess of Gd 3+ in the neutral solutions, the sorption capacity reaches 1.45 mmol(Gd 3+ )/g(GO). The effectiveness of water, hydrochloric acid and EDTA as desorbing eluents is compared. We experimentally demonstrate the existence of the Gd 3+ concentration gradient within the diffuse layer at the GO/water interface, and its exponential character on the distance from the GO surface. The thickness of the diffuse layer and the position of the slipping plane are estimated. Such characteristics, typical for colloid systems, show that in solutions, GO flakes form distinct phase, even though they are just one atom thick. Copyright © 2018 Elsevier Inc. All rights reserved.

Controlled Electrostatic Self-Assembly of Ibuprofen-Cationic Dextran Nanoconjugates Prepared by low Energy Green Process - a Novel Delivery Tool for Poorly Soluble Drugs.

PubMed

Abioye, Amos Olusegun; Kola-Mustapha, Adeola

2015-06-01

The direct effect of electrostatic interaction between ibuprofen and cationic dextran on the system-specific physicochemical parameters and intrinsic dissolution characteristics of ibuprofen was evaluated in order to develop drug-polymer nanoconjugate as a delivery strategy for poorly soluble drugs. Amorphous ibuprofen-DEAE dextran (Ddex) nanoconjugate was prepared using a low energy, controlled amphiphile-polyelectrolyte electrostatic self-assembly technique optimized by ibuprofen critical solubility and Ddex charge screening. Physicochemical characteristics of the nanoconjugates were evaluated using FTIR, DSC, TGA, NMR and SEM relative to pure ibuprofen. The in vitro release profiles and mechanism of ibuprofen release were determined using mathematical models including zero and first order kinetics; Higuchi; Hixson-Crowell and Korsmeyer-Peppas. Electrostatic interaction between ibuprofen and Ddex was confirmed with FT-IR, (1)H NMR and (13)C NMR spectroscopy. The broad and diffused DSC peaks of the nanoconjugate as well as the disappearance of ibuprofen melting peak provided evidence for their highly amorphous state. Low concentrations of Ddex up to 1.0 × 10(-6) g/dm(3) enhanced dissolution of ibuprofen to a maximum of 81.32% beyond which retardation occurred steadily. Multiple release mechanisms including diffusion; discrete drug dissolution; anomalous transport and super case II transport were noted. Controlled assembly of ibuprofen and Ddex produced a novel formulation with potential extended drug release dictated by Ddex concentration.

Effect of Ca substitution on some physical properties of nano-structured and bulk Ni-ferrite samples

NASA Astrophysics Data System (ADS)

Assar, S. T.; Abosheiasha, H. F.

2015-01-01

Nanoparticles of Ni1-xCaxFe2O4 (x=0.0, 0.02, 0.04, 0.06 and 0.10) were prepared by citrate precursor method. A part of these samples was sintered at 600 °C for 2 h in order to keep the particles within the nano-size while the other part was sintered at 1000 °C to let the particles to grow to the bulk size. The effect of Ca2+ ion substitution in nickel ferrite on some structural, magnetic, electrical and thermal properties was investigated. All samples were characterized by using X-ray diffraction (XRD), transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FTIR) and vibrating sample magnetometer (VSM). A two probe method was used to measure the dc electrical conductivity whereas the photoacoustic (PA) technique was used to determine the thermal diffusivity of the samples. To interpret different experimental results for nano and bulk samples some cation distributions were assumed based on the VSM and XRD data. These suggested cation distributions give logical explanations for other experimental results such as the observed values of the absorption bands in FTIR spectra and the dc conductivity results. Finally, in the thermal measurements it was found that increasing the Ca2+ ion content causes a decrease in the thermal diffusivity of both nano and bulk samples. The explanation of this behavior is ascribed to the phonon-phonon scattering.

The transepithelial transport mechanism of polybrominated diphenyl ethers in human intestine determined using a Caco-2 cell monolayer.

PubMed

Yu, Yingxin; Wang, Mengmeng; Zhang, Kaiqiong; Yang, Dan; Zhong, Yufang; An, Jing; Lei, Bingli; Zhang, Xinyu

2017-04-01

Oral ingestion plays an important role in human exposure to polybrominated diphenyl ethers (PBDEs). The uptake of PBDEs primarily occurs in the small intestine. The aim of the present study is to investigate the transepithelial transport characteristics and mechanisms of PBDEs in the small intestine using a Caco-2 cell monolayer model. The apparent permeability coefficients of PBDEs indicated that tri- to hepta-BDEs were poorly absorbed compounds. A linear increase in transepithelial transport was observed with various concentrations of PBDEs, which suggested that passive diffusion dominated their transport at the concentration range tested. In addition, the pseudo-first-order kinetics equation can be applied to the transepithelial transport of PBDEs. The rate-determining step in transepithelial transport of PBDEs was trans-cell transport including the trans-pore process. The significantly lower transepithelial transport rates at low temperature for bidirectional transepithelial transport suggested that an energy-dependent transport mechanism was involved. The efflux transporters (P-glycoprotein, multidrug resistance-associated protein, and breast cancer resistance protein) and influx transporters (organic cation transporters) participated in the transepithelial transport of PBDEs. In addition, the transepithelial transport of PBDEs was pH sensitive; however, more information is required to understand the influence of pH. Copyright © 2016 Elsevier Inc. All rights reserved.

Video imaging analysis of the plasma membrane permeabilizing effects of Bacillus thuringiensis insecticidal toxins in Sf9 cells.

PubMed

Villalon, M; Vachon, V; Brousseau, R; Schwartz, J L; Laprade, R

1998-01-05

The size and ionic selectivity of the pores formed by the insecticidal crystal protein Cry1C from Bacillus thuringiensis in the plasma membrane of Sf9 cells, an established cell line derived from the fall armyworm Spodoptera frugiperda, were analyzed with a video imaging technique. Changes in the permeability of the membrane were estimated from the rate of osmotic swelling of the cells. In the presence of Cry1C, which is toxic to Sf9 cells, the permeability of the cell membrane to KCl and glucose increased in a dose-dependent manner. In contrast, Cry1Aa, Cry1Ab and Cry1Ac, toxins to which Sf9 cells are not susceptible, had no detectable effect. Pores formed by Cry1C allowed the diffusion of sucrose, but were impermeable to the trisaccharide raffinose. On the basis of the hydrodynamic radii of these substances, the diameter of the pores was estimated to be 1.0-1.2 nm. In the presence of salts, the rate of swelling of cells exposed to Cry1C was about equally influenced by the size of the anion as by that of the cation, indicating that the ionic selectivity of the pores is low.

Interlayer-Spacing-Regulated VOPO4 Nanosheets with Fast Kinetics for High-Capacity and Durable Rechargeable Magnesium Batteries.

PubMed

Zhou, Limin; Liu, Qi; Zhang, Zihe; Zhang, Kai; Xiong, Fangyu; Tan, Shuangshuang; An, Qinyou; Kang, Yong-Mook; Zhou, Zhen; Mai, Liqiang

2018-06-25

Owing to the low-cost, safety, dendrite-free formation, and two-electron redox properties of magnesium (Mg), rechargeable Mg batteries are considered as promising next-generation secondary batteries with high specific capacity and energy density. However, the clumsy Mg 2+ with high polarity inclines to sluggish Mg insertion/deinsertion, leading to inadequate reversible capacity and rate performance. Herein, 2D VOPO 4 nanosheets with expanded interlayer spacing (1.42 nm) are prepared and applied in rechargeable magnesium batteries for the first time. The interlayer expansion provides enough diffusion space for fast kinetics of MgCl + ion flux with low polarization. Benefiting from the structural configuration, the Mg battery exhibits a remarkable reversible capacity of 310 mAh g -1 at 50 mA g -1 , excellent rate capability, and good cycling stability (192 mAh g -1 at 100 mA g -1 even after 500 cycles). In addition, density functional theory (DFT) computations are conducted to understand the electrode behavior with decreased MgCl + migration energy barrier compared with Mg 2+ . This approach, based on the regulation of interlayer distance to control cation insertion, represents a promising guideline for electrode material design on the development of advanced secondary multivalent-ion batteries. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of hierarchical mesoporous lithium nickel cobalt manganese oxide spheres with high rate capability for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Tong, Wei; Huang, Yudai; Cai, Yanjun; Guo, Yong; Wang, Xingchao; Jia, Dianzeng; Sun, Zhipeng; Pang, Weikong; Guo, Zaiping; Zong, Jun

2018-01-01

Hierarchical mesoporous LiNi1/3Co1/3Mn1/3O2 spheres have been synthesized by urea-assisted solvothermal method with adding Triton X-100. The structure and morphology of the as-prepared materials were analyzed by X-ray diffraction and electron microscope. The results show that the as-prepared samples can be indexed as hexagonal layered structure with hierarchical architecture, and the possible formation mechanism is speculated. When evaluated as cathode material, the hierarchical mesoporous LiNi1/3Co1/3Mn1/3O2 spheres show good electrochemical properties with high initial discharge capacity of 129.9 mAh g-1, and remain the discharge capacity of 95.5 mAh g-1 after 160 cycles at 10C. The excellent electrochemical performance of the as-prepared sample can be attributed to its stable hierarchical mesoporous framework in conjunction with large specific surface, low cation mixing and small particle size. They not only provide a large number of reaction sites for surface or interface reaction, but also shorten the diffusion length of Li+ ions. Meanwhile, the mesoporous spheres composed of nanoparticles can contribute to high rate ability and buffer volume changes during charge/discharge process.

Simultaneous Analysis of Monovalent Anions and Cations with a Sub-Microliter Dead-Volume Flow-Through Potentiometric Detector for Ion Chromatography

PubMed Central

Dumanli, Rukiye; Attar, Azade; Erci, Vildan; Isildak, Ibrahim

2016-01-01

A microliter dead-volume flow-through cell as a potentiometric detector is described in this article for sensitive, selective and simultaneous detection of common monovalent anions and cations in single column ion chromatography for the first time. The detection cell consisted of less selective anion- and cation-selective composite membrane electrodes together with a solid-state composite matrix reference electrode. The simultaneous separation and sensitive detection of sodium (Na+), potassium (K+), ammonium (NH4+), chloride (Cl−) and nitrate (NO3−) in a single run was achieved by using 98% 1.5 mM MgSO4 and 2% acetonitrile eluent with a mixed-bed ion-exchange separation column without suppressor column system. The separation and simultaneous detection of the anions and cations were completed in 6 min at the eluent flow-rate of 0.8 mL/min. Detection limits, at S/N = 3, were ranged from 0.2 to 1.0 µM for the anions and 0.3 to 3.0 µM for the cations, respectively. The developed method was successfully applied to the simultaneous determination of monovalent anions and cations in several environmental and biological samples. PMID:26786906

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

PubMed

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

2014-11-21

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

Random-walk diffusion and drying of porous materials

NASA Astrophysics Data System (ADS)

Mehrafarin, M.; Faghihi, M.

2001-12-01

Based on random-walk diffusion, a microscopic model for drying is proposed to explain the characteristic features of the drying-rate curve of porous materials. The constant drying-rate period is considered as a normal diffusion process. The transition to the falling-rate regime is attributed to the fractal nature of porous materials which results in crossover to anomalous diffusion.

Multiscale Modeling of Diffusion in a Crowded Environment.

PubMed

Meinecke, Lina

2017-11-01

We present a multiscale approach to model diffusion in a crowded environment and its effect on the reaction rates. Diffusion in biological systems is often modeled by a discrete space jump process in order to capture the inherent noise of biological systems, which becomes important in the low copy number regime. To model diffusion in the crowded cell environment efficiently, we compute the jump rates in this mesoscopic model from local first exit times, which account for the microscopic positions of the crowding molecules, while the diffusing molecules jump on a coarser Cartesian grid. We then extract a macroscopic description from the resulting jump rates, where the excluded volume effect is modeled by a diffusion equation with space-dependent diffusion coefficient. The crowding molecules can be of arbitrary shape and size, and numerical experiments demonstrate that those factors together with the size of the diffusing molecule play a crucial role on the magnitude of the decrease in diffusive motion. When correcting the reaction rates for the altered diffusion we can show that molecular crowding either enhances or inhibits chemical reactions depending on local fluctuations of the obstacle density.

Effect of Drag Reducing Polymer and Suspended Solid on the Rate of Diffusion Controlled Corrosion in 90° Copper Elbow

NASA Astrophysics Data System (ADS)

Fouad, Mohamed Ahmed; Zewail, Taghreed Mohamed; Amine, Nieven Kamal Abbes

2017-06-01

Rate of diffusion controlled corrosion in 90° Copper Elbow acidified dichromate has been investigated in relation to the following parameters: effect of solution velocity in the absence and presence of drag- reducing polymer on the rate of diffusion controlled corrosion, and effect of the presence of suspended solids on the rate of diffusion controlled corrosion. It was found that the presence of drag reducing polymer inhibited the rate of mass transfer, while the presence of suspended solid increased significantly the rate of mass transfer.

Molecules in motion: influences of diffusion on metabolic structure and function in skeletal muscle

PubMed Central

Kinsey, Stephen T.; Locke, Bruce R.; Dillaman, Richard M.

2011-01-01

Metabolic processes are often represented as a group of metabolites that interact through enzymatic reactions, thus forming a network of linked biochemical pathways. Implicit in this view is that diffusion of metabolites to and from enzymes is very fast compared with reaction rates, and metabolic fluxes are therefore almost exclusively dictated by catalytic properties. However, diffusion may exert greater control over the rates of reactions through: (1) an increase in reaction rates; (2) an increase in diffusion distances; or (3) a decrease in the relevant diffusion coefficients. It is therefore not surprising that skeletal muscle fibers have long been the focus of reaction–diffusion analyses because they have high and variable rates of ATP turnover, long diffusion distances, and hindered metabolite diffusion due to an abundance of intracellular barriers. Examination of the diversity of skeletal muscle fiber designs found in animals provides insights into the role that diffusion plays in governing both rates of metabolic fluxes and cellular organization. Experimental measurements of metabolic fluxes, diffusion distances and diffusion coefficients, coupled with reaction–diffusion mathematical models in a range of muscle types has started to reveal some general principles guiding muscle structure and metabolic function. Foremost among these is that metabolic processes in muscles do, in fact, appear to be largely reaction controlled and are not greatly limited by diffusion. However, the influence of diffusion is apparent in patterns of fiber growth and metabolic organization that appear to result from selective pressure to maintain reaction control of metabolism in muscle. PMID:21177946

Machine learning and linear regression models to predict catchment-level base cation weathering rates across the southern Appalachian Mountain region, USA

Treesearch

Nicholas A. Povak; Paul F. Hessburg; Todd C. McDonnell; Keith M. Reynolds; Timothy J. Sullivan; R. Brion Salter; Bernard J. Crosby

2014-01-01

Accurate estimates of soil mineral weathering are required for regional critical load (CL) modeling to identify ecosystems at risk of the deleterious effects from acidification. Within a correlative modeling framework, we used modeled catchment-level base cation weathering (BCw) as the response variable to identify key environmental correlates and predict a continuous...

Role of monovalent cations in fluid secretion from the exocrine rabbit pancreas.

PubMed

Kuijpers, G A; Van Nooy, I G; De Pont, J J

1989-08-21

The role of Na+ in fluid secretion by the isolated rabbit pancreas was investigated. The fluid secretion rate is reduced upon replacement of Na+ in the bathing medium by Li+, K+ or choline. The inhibition depends on the nature of the substituting cation, and is largest with choline. Upon replacement, the substituent cation appears in the secreted fluid, and the Na+ concentration in the secreted fluid is decreased in a mirror-like fashion. When Na+ is replaced by Li+ or choline, the secretory Na+ concentration is decreased, although less than in the bathing medium, and the K+ concentration is increased. When Na+ is replaced by K+, the Na+ and the K+ concentration in the secreted fluid are approximately equal to their bathing medium concentrations. In the Li+ and choline medium, stimulation of the pancreas by carbachol or CCK-8 increases the fluid secretion rate. In addition, it increases the Li+ or choline concentration, and decreases the Na+ and K+ concentrations in the secreted fluid. In normal and K+ medium, stimulation causes only a slight increase in fluid secretion rate, with no change in the secretory Na+ concentration. In normal medium, stimulation leads to a decrease in the secretory K+ concentration. The effects of replacing Na+ appear to be the result of a direct inhibition of the active HCO3- transport underlying secretion, and an indirect inhibition related to the permeability of the pancreas for the various cations. The stimulants are likely to act by increasing the permeability of the tight junctions.

Site identity and importance in cosubstituted bixbyite In 2O 3

DOE PAGES

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

2017-02-09

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

Site identity and importance in cosubstituted bixbyite In 2O 3

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

Rickert, Karl; Harris, Jeremy; Sedefoglu, Nazmi

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

Calcium Uptake by Excised Maize Roots and Interactions With Alkali Cations 1

PubMed Central

Maas, E. V.

1969-01-01

Ca2+ uptake was studied in short-term experiments using 5-day-old excised maize roots. This tissue readily absorbs Ca2+, and inhibition by dinitrophenol and low temperature shows that the process is metabolically mediated. The uptake of Ca2+, like that of other cations, is influenced by the counter ion, the pH and concentration of the ambient solution, and the presence of other cations. The rate of uptake from various salts decreases in the following order: NO3− > Cl− = Br− > SO42−. K+ and H+ greatly interfere with Ca2+ absorption, while Li+ and Na+ have only slight effects. PMID:16657169

Electrochemistry of Europium(III) Chloride in 3 LiCl – NaCl, 3 LiCl – 2 KCl, LiCl – RbCl, and 3 LiCl – 2 CsCl Eutectics at Various Temperatures

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

Schroll, Cynthia A.; Chatterjee, Sayandev; Levitskaia, Tatiana G.

Here we report the effect of changing the eutectic melt composition on the electrochemical properties of europium(III) chloride under pyroprocessing conditions. The number of electrons transferred, redox potentials and diffusion coefficients were determined using various electrochemical and spectroelectrochemical techniques in four different eutectic mixtures (3 LiCl - NaCl, 3 LiCl - 2 KCl, 3 LiCl - RbCl, and 3 LiCl - 2 CsCl) while varying the temperature of the melt. It was determined that Eu3+ undergoes a one electron reduction to Eu2+ in each melt at all temperatures evaluated. Within all the melts a positive shift in the redox potentialmore » as well as an increase in the diffusion coefficient for Eu3+ was observed as the temperature increased. Also observed was a positive shift in the redox potential and increase in the diffusion coefficient for Eu3+ as the weighted average of the cationic radii for the melt decreased.« less

Retention modeling for ultra-thin density of Cu-based conductive bridge random access memory (CBRAM)

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

Aga, Fekadu Gochole; Woo, Jiyong; Lee, Sangheon

We investigate the effect of Cu concentration On-state resistance retention characteristics of W/Cu/Ti/HfO{sub 2}/Pt memory cell. The development of RRAM device for application depends on the understanding of the failure mechanism and the key parameters for device optimization. In this study, we develop analytical expression for cations (Cu{sup +}) diffusion model using Gaussian distribution for detailed analysis of data retention time at high temperature. It is found that the improvement of data retention time depends not only on the conductive filament (CF) size but also on Cu atoms concentration density in the CF. Based on the simulation result, better datamore » retention time is observed for electron wave function associated with Cu{sup +} overlap and an extended state formation. This can be verified by analytical calculation of Cu atom defects inside the filament, based on Cu{sup +} diffusion model. The importance of Cu diffusion for the device reliability and the corresponding local temperature of the filament were analyzed by COMSOL Multiphysics simulation.« less

Transcriptional Analysis of Four Family 4 P450s in a Puerto Rico Strain of Aedes aegypti (Diptera: Culicidae) Compared With an Orlando Strain and Their Possible Functional Roles in Permethrin Resistance

DTIC Science & Technology

2014-05-01

melanogaster expressing CYP4D24, CYP4H29, CYP4J15v1, and CYP4H33 had a survival rate of 60.0 6.7, 29.0 4.4, 64.4 9.7, and 11.0 4.4...CYP4D24 and CYP4H29 had a survival rate of 37.8 4.4 and 2.2 2.2%, respectively. Taken together, our results suggest that CYP4D24 might play an...mechanisms, including target site insensitivity, reduced penetration rate , and met- abolic detoxiÞcation. In the case of metabolic detox- iÞcation

Overcharging below the nanoscale: Multivalent cations reverse the ion selectivity of a biological channel

NASA Astrophysics Data System (ADS)

García-Giménez, Elena; Alcaraz, Antonio; Aguilella, Vicente M.

2010-02-01

We report charge inversion within a nanoscopic biological protein ion channel in salts of multivalent ions. The presence of positive divalent and trivalent counterions reverses the cationic selectivity of the OmpF channel, a general diffusion porin located in the outer membrane of E. coli. We discuss the conditions under which charge inversion can be inferred from the change in sign of the measured quantity, the channel zero current potential. By comparing experimental results in protein channels whose charge has been modified after site-directed mutagenesis, the predictions of current theories of charge inversion are critically examined. It is emphasized that charge inversion does not necessarily increase with the bare surface charge density of the interface and that even this concept of surface charge density may become meaningless in some biological ion channels. Thus, any theory based on electrostatic correlations or chemical binding should explicitly take into account the particular structure of the charged interface.

Atomic origins of water-vapour-promoted alloy oxidation

NASA Astrophysics Data System (ADS)

Luo, Langli; Su, Mao; Yan, Pengfei; Zou, Lianfeng; Schreiber, Daniel K.; Baer, Donald R.; Zhu, Zihua; Zhou, Guangwen; Wang, Yanting; Bruemmer, Stephen M.; Xu, Zhijie; Wang, Chongmin

2018-06-01

The presence of water vapour, intentional or unavoidable, is crucial to many materials applications, such as in steam generators, turbine engines, fuel cells, catalysts and corrosion1-4. Phenomenologically, water vapour has been noted to accelerate oxidation of metals and alloys5,6. However, the atomistic mechanisms behind such oxidation remain elusive. Through direct in situ atomic-scale transmission electron microscopy observations and density functional theory calculations, we reveal that water-vapour-enhanced oxidation of a nickel-chromium alloy is associated with proton-dissolution-promoted formation, migration, and clustering of both cation and anion vacancies. Protons derived from water dissociation can occupy interstitial positions in the oxide lattice, consequently lowering vacancy formation energy and decreasing the diffusion barrier of both cations and anions, which leads to enhanced oxidation in moist environments at elevated temperatures. This work provides insights into water-vapour-enhanced alloy oxidation and has significant implications in other material and chemical processes involving water vapour, such as corrosion, heterogeneous catalysis and ionic conduction.

Systematic computational and experimental investigation of lithium-ion transport mechanisms in polyester-based polymer electrolytes

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

Webb, Michael A.; Jung, Yukyung; Pesko, Danielle M.

Understanding the mechanisms of lithium-ion transport in polymers is crucial for the design of polymer electrolytes. We combine modular synthesis, electrochemical characterization, and molecular simulation to investigate lithium-ion transport in a new family of polyester-based polymers and in poly(ethylene oxide) (PEO). Theoretical predictions of glass-transition temperatures and ionic conductivities in the polymers agree well with experimental measurements. Interestingly, both the experiments and simulations indicate that the ionic conductivity of PEO, relative to the polyesters, is far higher than would be expected from its relative glass-transition temperature. The simulations reveal that diffusion of the lithium cations in the polyesters proceeds viamore » a different mechanism than in PEO, and analysis of the distribution of available cation solvation sites in the various polymers provides a novel and intuitive way to explain the experimentally observed ionic conductivities. This work provides a platform for the evaluation and prediction of ionic conductivities in polymer electrolyte materials.« less

The structure feature of layered M1/3TiNbO5 (M=Fe, Ce) and their photocatalytic oxidization performance for ethyl mercaptan

NASA Astrophysics Data System (ADS)

Dong, Rui; Wang, Yuan; Wang, Ningning; Xu, Lei; He, Jie; Wu, Shanshan; Lan, Yunxiang; Hu, Jinsong

2016-09-01

Layered photocatalytic materials M1/3TiNbO5 (M = Fe, Ce) were prepared by ion-exchange of KTiNbO5 with M(NO3)3. The parent KTiNbO5 was synthesized with titanium (IV) isopropoxide and niobium oxalate by a novel polymerized complex (PC) method. The micro-structures and spectral response features of the as-prepared samples were characterized by powder X-ray diffraction (XRD), transmission electron microscope (TEM), laser Raman spectroscopy (LRS) and UV-vis diffuse reflectance spectroscopy (UV-vis DRS). The results revealed that there was a significant interaction between the interlayer cation and the terminal Nbdbnd O (Tidbnd O) bond in the NbO6 (TiO6) unit of the laminates. Photocatalytic performance was evaluated in oxidation of ethyl mercaptan under natural and UV light irradiation. It can be deduced that the photocatalytic oxidization performance can be directly affected by the characteristics of the interlayer cations.

Microstructure of room temperature ionic liquids at stepped graphite electrodes

DOE PAGES

Feng, Guang; Li, Song; Zhao, Wei; ...

2015-07-14

Molecular dynamics simulations of room temperature ionic liquid (RTIL) [emim][TFSI] at stepped graphite electrodes were performed to investigate the influence of the thickness of the electrode surface step on the microstructure of interfacial RTILs. A strong correlation was observed between the interfacial RTIL structure and the step thickness in electrode surface as well as the ion size. Specifically, when the step thickness is commensurate with ion size, the interfacial layering of cation/anion is more evident; whereas, the layering tends to be less defined when the step thickness is close to the half of ion size. Furthermore, two-dimensional microstructure of ionmore » layers exhibits different patterns and alignments of counter-ion/co-ion lattice at neutral and charged electrodes. As the cation/anion layering could impose considerable effects on ion diffusion, the detailed information of interfacial RTILs at stepped graphite presented here would help to understand the molecular mechanism of RTIL-electrode interfaces in supercapacitors.« less

Effect of polacrilin potassium as disintegrant on bioavailability of diclofenac potassium in tablets : a technical note.

PubMed

Bele, Mrudula H; Derle, Diliprao V

2012-09-01

Polacrilin potassium is an ion exchange resin used in oral pharmaceutical formulations as a tablet disintegrant. It is a weakly acidic cation exchange resin. Chemically, it is a partial potassium salt of a copolymer of methacrylic acid with divinyl benzene. It ionizes to an anionic polymer chain and potassium cations. It was hypothesized that polacrilin potassium may be able to improve the permeability of anionic drugs according to the Donnan membrane phenomenon. The effect of polacrilin potassium on the permeability of diclofenac potassium, used as a model anionic drug, was tested in vitro using diffusion cells and in vivo by monitoring serum levels in rats. The amount of drug permeated across a dialysis membrane in vitro was significantly more in the presence of polacrilin potassium. Significant improvement was found in the extent of drug absorption in vivo. It could be concluded that polacrilin potassium may be used as a high-functionality excipient for improving the bioavailability of anionic drugs having poor gastrointestinal permeability.

Optical Absorptions of Oxygenated Carbon Chain Cations in the Gas Phase

NASA Astrophysics Data System (ADS)

Hardy, F.-X.; Rice, C. A.; Chakraborty, A.; Fulara, J.; Maier, J. P.

2016-06-01

The gas-phase electronic spectra of linear OC4O+ and a planar C6H2O+ isomer were obtained at a rotational temperature of ≈10 K. Absorption measurements in a 6 K neon matrix were followed by gas-phase observations in a cryogenic radiofrequency ion trap. The origin bands of the 1{}2{{{\\Pi }}}u ≤ftarrow X{}2{{{\\Pi }}}g transition of OC4O+ and the 1{}2A{}2 ≤ftarrow X{}2B1 of HCCC(CO)CCH+ lie at 417.31 ± 0.01 nm and 523.49 ± 0.01 nm, respectively. These constitute the first electronic spectra of oxygenated carbon chain cations studied under conditions that are relevant to the diffuse interstellar bands (DIBs), as both have a visible transition. The recent analysis of the 579.5 nm DIB indicates that small carriers, five to seven heavy atoms, continue to be possible candidates (Huang & Oka 2015). Astronomical implications are discussed regarding this kind of oxygenated molecules.

Gas-phase Absorptions of {{\\rm{C}}}_{42}{{\\rm{H}}}_{18}^{+} near 8300 Å below 10 K: Astronomical Implications

NASA Astrophysics Data System (ADS)

Campbell, E. K.; Maier, J. P.

2017-11-01

The gas-phase electronic spectrum of {{{C}}}42{{{H}}}18+ ({{HBC}}+) with an origin band at 8281 \\mathringA has been measured below 10 {{K}} by photofragmentation of helium complexes ({{{C}}}42{{{H}}}18+{--}{{He}}n) in a radiofrequency trap. {{HBC}}+ is a medium-sized polycyclic aromatic hydrocarbon (PAH) cation, and using an ion trapping technique it has been possible to record a high-quality gas-phase spectrum to directly compare with astronomical observations. No diffuse interstellar bands (DIBs) have been reported at the wavelengths of the strongest absorption bands in the {{{C}}}42{{{H}}}18+ spectrum. Measurement of absolute absorption cross sections in the ion trap allows upper limits to the column density of this ion to be {10}12 {{cm}}-2, indicating that even PAH cations of this size, which are believed to be stable in the interstellar medium, should be excluded as candidates for at least the strong DIBs.

A2TiF 5· nH 2O ( A=K, Rb, or Cs; n=0 or 1): Synthesis, structure, characterization, and calculations of three new uni-dimensional titanium fluorides

NASA Astrophysics Data System (ADS)

Jo, Vinna; Woo Lee, Dong; Koo, Hyun-Joo; Ok, Kang Min

2011-04-01

Three new uni-dimensional alkali metal titanium fluoride materials, A2TiF 5· nH 2O ( A=K, Rb, or Cs; n=0 or 1) have been synthesized by hydrothermal reactions. The structures of A2TiF 5· nH 2O have been determined by single-crystal X-ray diffraction. The Ti 4+ cations have been reduced to Ti 3+ during the synthesis reactions. All three A2TiF 5· nH 2O materials contain novel 1-D chain structures that are composed of the slightly distorted Ti 3+F 6 corner-sharing octahedra attributable to the Jahn-Teller distortion. The coordination environment of the alkali metal cations plays an important role to determine the degree of turning in the chain structures. Complete structural analyses, Infrared and UV-vis diffuse reflectance spectra, and thermal analyses are presented, as are electronic structure calculations.

Systematic computational and experimental investigation of lithium-ion transport mechanisms in polyester-based polymer electrolytes

DOE PAGES

Webb, Michael A.; Jung, Yukyung; Pesko, Danielle M.; ...

2015-07-10

Understanding the mechanisms of lithium-ion transport in polymers is crucial for the design of polymer electrolytes. We combine modular synthesis, electrochemical characterization, and molecular simulation to investigate lithium-ion transport in a new family of polyester-based polymers and in poly(ethylene oxide) (PEO). Theoretical predictions of glass-transition temperatures and ionic conductivities in the polymers agree well with experimental measurements. Interestingly, both the experiments and simulations indicate that the ionic conductivity of PEO, relative to the polyesters, is far higher than would be expected from its relative glass-transition temperature. The simulations reveal that diffusion of the lithium cations in the polyesters proceeds viamore » a different mechanism than in PEO, and analysis of the distribution of available cation solvation sites in the various polymers provides a novel and intuitive way to explain the experimentally observed ionic conductivities. This work provides a platform for the evaluation and prediction of ionic conductivities in polymer electrolyte materials.« less

Understanding Tribofilm Formation Mechanisms in Ionic Liquid Lubrication

DOE PAGES

Zhou, Yan; Leonard, Donovan N.; Guo, Wei; ...

2017-08-16

Ionic liquids (ILs) have recently been developed as a novel class of lubricant anti-wear (AW) additives, but the formation mechanism of their wear protective tribofilms is not yet well understood. Unlike the conventional metal-containing AW additives that self-react to grow a tribofilm, the metal-free ILs require a supplier of metal cations in the tribofilm growth. The two apparent sources of metal cations are the contact surface and the wear debris, and the latter contains important ‘historical’ interface information but often is overlooked. We correlated the morphological and compositional characteristics of tribofilms and wear debris from an IL-lubricated steel–steel contact. Inmore » conclusion, a complete multi-step formation mechanism is proposed for the tribofilm of metal-free AW additives, including direct tribochemical reactions between the metallic contact surface with oxygen to form an oxide interlayer, wear debris generation and breakdown, tribofilm growth via mechanical deposition, chemical deposition, and oxygen diffusion.« less

Hydrodynamic interpretation on the rotational diffusion of peroxylamine disulfonate solute dissolved in room temperature ionic liquids as studied by electron paramagnetic resonance spectroscopy.

PubMed

Miyake, Yusuke; Akai, Nobuyuki; Kawai, Akio; Shibuya, Kazuhiko

2011-06-23

Rotational motion of a nitroxide radical, peroxylamine disulfonate (PADS), dissolved in room temperature ionic liquids (RTILs) was studied by analyzing electron paramagnetic resonance spectra of PADS in various RTILs. We determined physical properties of PADS such as the hyperfine coupling constant (A), the temperature dependence of anisotropic rotational correlation times (τ(∥) and τ(⊥)), and rotational anisotropy (N). We observed that the A values remain unchanged for various RTILs, which indicates negligible interaction between the N-O PADS group and the cation of RTIL. Large N values suggest strong interaction of the negative sulfonyl parts of PADS with the cations of RTILs. Most of the τ(∥), τ(⊥), and (τ(∥)τ(⊥))(1/2) values are within the range calculated on the basis of a hydrodynamic theory with stick and slip boundary conditions. It was deduced that this theory could not adequately explain the measured results in some RTILs with smaller BF(4) and PF(6) anions.

Systematic Computational and Experimental Investigation of Lithium-Ion Transport Mechanisms in Polyester-Based Polymer Electrolytes

PubMed Central

2015-01-01

Understanding the mechanisms of lithium-ion transport in polymers is crucial for the design of polymer electrolytes. We combine modular synthesis, electrochemical characterization, and molecular simulation to investigate lithium-ion transport in a new family of polyester-based polymers and in poly(ethylene oxide) (PEO). Theoretical predictions of glass-transition temperatures and ionic conductivities in the polymers agree well with experimental measurements. Interestingly, both the experiments and simulations indicate that the ionic conductivity of PEO, relative to the polyesters, is far higher than would be expected from its relative glass-transition temperature. The simulations reveal that diffusion of the lithium cations in the polyesters proceeds via a different mechanism than in PEO, and analysis of the distribution of available cation solvation sites in the various polymers provides a novel and intuitive way to explain the experimentally observed ionic conductivities. This work provides a platform for the evaluation and prediction of ionic conductivities in polymer electrolyte materials. PMID:27162971

Atomic origins of water-vapour-promoted alloy oxidation.

PubMed

Luo, Langli; Su, Mao; Yan, Pengfei; Zou, Lianfeng; Schreiber, Daniel K; Baer, Donald R; Zhu, Zihua; Zhou, Guangwen; Wang, Yanting; Bruemmer, Stephen M; Xu, Zhijie; Wang, Chongmin

2018-06-01

The presence of water vapour, intentional or unavoidable, is crucial to many materials applications, such as in steam generators, turbine engines, fuel cells, catalysts and corrosion 1-4 . Phenomenologically, water vapour has been noted to accelerate oxidation of metals and alloys 5,6 . However, the atomistic mechanisms behind such oxidation remain elusive. Through direct in situ atomic-scale transmission electron microscopy observations and density functional theory calculations, we reveal that water-vapour-enhanced oxidation of a nickel-chromium alloy is associated with proton-dissolution-promoted formation, migration, and clustering of both cation and anion vacancies. Protons derived from water dissociation can occupy interstitial positions in the oxide lattice, consequently lowering vacancy formation energy and decreasing the diffusion barrier of both cations and anions, which leads to enhanced oxidation in moist environments at elevated temperatures. This work provides insights into water-vapour-enhanced alloy oxidation and has significant implications in other material and chemical processes involving water vapour, such as corrosion, heterogeneous catalysis and ionic conduction.

Understanding Tribofilm Formation Mechanisms in Ionic Liquid Lubrication

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

Zhou, Yan; Leonard, Donovan N.; Guo, Wei

Ionic liquids (ILs) have recently been developed as a novel class of lubricant anti-wear (AW) additives, but the formation mechanism of their wear protective tribofilms is not yet well understood. Unlike the conventional metal-containing AW additives that self-react to grow a tribofilm, the metal-free ILs require a supplier of metal cations in the tribofilm growth. The two apparent sources of metal cations are the contact surface and the wear debris, and the latter contains important ‘historical’ interface information but often is overlooked. We correlated the morphological and compositional characteristics of tribofilms and wear debris from an IL-lubricated steel–steel contact. Inmore » conclusion, a complete multi-step formation mechanism is proposed for the tribofilm of metal-free AW additives, including direct tribochemical reactions between the metallic contact surface with oxygen to form an oxide interlayer, wear debris generation and breakdown, tribofilm growth via mechanical deposition, chemical deposition, and oxygen diffusion.« less

Multiscale diffusion in the mitotic Drosophila melanogaster syncytial blastoderm

PubMed Central

Daniels, Brian R.; Rikhy, Richa; Renz, Malte; Dobrowsky, Terrence M.; Lippincott-Schwartz, Jennifer

2012-01-01

Despite the fundamental importance of diffusion for embryonic morphogen gradient formation in the early Drosophila melanogaster embryo, there remains controversy regarding both the extent and the rate of diffusion of well-characterized morphogens. Furthermore, the recent observation of diffusional “compartmentalization” has suggested that diffusion may in fact be nonideal and mediated by an as-yet-unidentified mechanism. Here, we characterize the effects of the geometry of the early syncytial Drosophila embryo on the effective diffusivity of cytoplasmic proteins. Our results demonstrate that the presence of transient mitotic membrane furrows results in a multiscale diffusion effect that has a significant impact on effective diffusion rates across the embryo. Using a combination of live-cell experiments and computational modeling, we characterize these effects and relate effective bulk diffusion rates to instantaneous diffusion coefficients throughout the syncytial blastoderm nuclear cycle phase of the early embryo. This multiscale effect may be related to the effect of interphase nuclei on effective diffusion, and thus we propose that an as-yet-unidentified role of syncytial membrane furrows is to temporally regulate bulk embryonic diffusion rates to balance the multiscale effect of interphase nuclei, which ultimately stabilizes the shapes of various morphogen gradients. PMID:22592793

A spatial and seasonal assessment of river water chemistry across North West England.

PubMed

Rothwell, J J; Dise, N B; Taylor, K G; Allott, T E H; Scholefield, P; Davies, H; Neal, C

2010-01-15

This paper presents information on the spatial and seasonal patterns of river water chemistry at approximately 800 sites in North West England based on data from the Environment Agency regional monitoring programme. Within a GIS framework, the linkages between average water chemistry (pH, sulphate, base cations, nutrients and metals) catchment characteristics (topography, land cover, soil hydrology, base flow index and geology), rainfall, deposition chemistry and geo-spatial information on discharge consents (point sources) are examined. Water quality maps reveal that there is a clear distinction between the uplands and lowlands. Upland waters are acidic and have low concentrations of base cations, explained by background geological sources and land cover. Localised high concentrations of metals occur in areas of the Cumbrian Fells which are subjected to mining effluent inputs. Nutrient concentrations are low in the uplands with the exception sites receiving effluent inputs from rural point sources. In the lowlands, both past and present human activities have a major impact on river water chemistry, especially in the urban and industrial heartlands of Greater Manchester, south Lancashire and Merseyside. Over 40% of the sites have average orthophosphate concentrations >0.1mg-Pl(-1). Results suggest that the dominant control on orthophosphate concentrations is point source contributions from sewage effluent inputs. Diffuse agricultural sources are also important, although this influence is masked by the impact of point sources. Average nitrate concentrations are linked to the coverage of arable land, although sewage effluent inputs have a significant effect on nitrate concentrations. Metal concentrations in the lowlands are linked to diffuse and point sources. The study demonstrates that point sources, as well as diffuse sources, need to be considered when targeting measures for the effective reduction in river nutrient concentrations. This issue is clearly important with regards to the European Union Water Framework Directive, eutrophication and river water quality. Copyright 2009 Elsevier B.V. All rights reserved.

Gas Phase Absorption Spectroscopy of C+60 and C+70 in a Cryogenic Ion Trap: Comparison with Astronomical Measurements

NASA Astrophysics Data System (ADS)

Campbell, E. K.; Holz, M.; Maier, J. P.; Gerlich, D.; Walker, G. A. H.; Bohlender, D.

2016-05-01

Recent low-temperature laboratory measurements and astronomical observations have proved that the fullerene cation {{{C}}}60+ is responsible for four diffuse interstellar bands (DIBs). These absorptions correspond to the strongest bands of the lowest electronic transition. The gas phase spectrum below 10 {{K}} is reported here for the full wavelength range encompassed by the electronic transition. The absorption spectrum of {{{C}}}70+, with its origin band at 7959.2 {{\\mathringA }}, has been obtained under similar laboratory conditions. Observations made toward the reddened star {HD} 183143 were used in a specific search for the absorption of these fullerene cations in diffuse clouds. In the case of {{{C}}}60+, one further band in the astronomical spectrum at 9348.5 \\mathringA is identified, increasing the total number of assigned DIBs to five. Numerous other {{{C}}}60+ absorptions in the laboratory spectrum are found to lie below the astronomical detection limit. Special emphasis is placed on the laboratory determination of absolute absorption cross-sections. For {{{C}}}60+ this directly yields a column density, N({{{C}}}60+), of 2× {10}13 {{{cm}}}-2 in diffuse clouds, without the need to rely on theoretical oscillator strengths. The intensity of the {{{C}}}70+ electronic transition in the range 7000-8000 Å is spread over many features of similar strength. Absorption cross-section measurements indicate that even for a similar column density, the individual absorption bands of {{{C}}}70+ will be too weak to be detected in the astronomical spectra, which is confirmed giving an upper limit of 2 {{m\\mathringA }} to the equivalent width. Based on observations obtained at the Canada-France-Hawaii Telescope (CFHT) which is operated by the National Research Council of Canada, the Institut National des Sciences de l’Univers of the Centre National de la Recherche Scientifique of France, and the University of Hawaii.

Two-Oxide Disequilibrium: A New Geospeedometer Based on Diffusion in Ilmenite

NASA Astrophysics Data System (ADS)

Williams, K. B.; Krawczynski, M. J.; Van Orman, J. A.

2016-12-01

Diffusion-annealing experiments were conducted in a 0.5" piston cylinder apparatus to investigate diffusivity of Fe2+, Mg2+, and Mn2+ in ilmenite solid solutions between 800ºC and 1000ºC. Polycrystalline ilmenite (FeTiO3) was juxtaposed against either an oriented geikielite (MgTiO3) single crystal or polycrystalline Mn-bearing (5 mol% Mn) ilmenite, in a "diffusion-couple" geometry. Geikielite single crystals were synthesized at Los Alamos National Laboratory, cut into 1 mm edge-length cubes, and polished either perpendicular or parallel to the c-axis. Polycrystalline ilmenite starting materials were synthesized by mixing high purity reagent-grade oxides (FeO, MnO, and TiO2) and sintering in a piston cylinder apparatus, then cut into wafers and polished. Experimental run products were analyzed by electron microprobe at Washington University in St. Louis. Microprobe analyses were obtained perpendicularly across the diffusion interface for each experiment. Experimental diffusion profiles create smooth curves that, when fit with an error function, define Fe-Mg and Fe-Mn interdiffusion coefficients in ilmenite. The diffusion coefficients do not appear compositionally dependent, but do show significant anisotropy. Preliminary results suggest diffusion activation energies are lower in ilmenite than in titanomagnetite [1]. Ilmenite-titanomagnetite equilibria define pre-eruptive temperatures and oxygen fugacities. However, oxides often exist out of equilibrium [2]. We use the cation diffusion data for ilmenite and existing data on titanomagnetite to establish two-oxide disequilibrium as a geospeedometer. Our data constrain oxide-oxide re-equilibration timescales at Mt. Unzen to months, consistent with estimates from zoned, single crystals of magnetite [3,4]. Future experiments will examine the effect of oxygen fugacity on diffusivity in ilmenite solid solutions. References:[1] Van Orman & Crispin (2010) RiMG 72, 757-825.[2] Bacon & Hirschmann (1988) Am. Min. 73, 57-61.[3] Nakamura (1995) Geology 23, 807-810.[4] Venezky & Rutherford (1999) J. Volc. Geo. Res. 89, 213-230.

The effect of cation:anion ratio in solution on the mechanism of barite growth at constant supersaturation: Role of the desolvation process on the growth kinetics

NASA Astrophysics Data System (ADS)

Kowacz, M.; Putnis, C. V.; Putnis, A.

2007-11-01

The mechanism of barite growth has been investigated in a fluid cell of an Atomic Force Microscope by passing solutions of constant supersaturation ( Ω) but variable ion activity ratio ( r=a/a) over a barite substrate.The observed dependence of step-spreading velocity on solution stoichiometry can be explained by considering non-equivalent attachment frequency factors for the cation and anion. We show that the potential for two-dimensional nucleation changes under a constant thermodynamic driving force due to the kinetics of barium integration into the surface, and that the growth mode changes from preexisting step advancement to island spreading as the cation/anion activity ratio increases. Scanning electron microscopy studies of crystals grown in bulk solutions support our findings that matching the ion ratio in the fluid to that of the crystal lattice does not result in maximum growth and nucleation rates. Significantly more rapid rates correspond to solution stoichiometries where [Ba 2+] is in excess with respect to [ SO42-]. Experiments performed in dilute aqueous solutions of methanol show that even 0.02 molar fraction of organic cosolvent in the growth solution significantly accelerates step growth velocity and nucleation rates (while keeping Ω the same as in the reference solution in water). Our observations suggest that the effect of methanol on barite growth results first of all from reduction of the barrier that prevents the Ba 2+ from reaching the surface and corroborate the hypothesis that desolvation of the cation and of the surface is the rate limiting kinetic process for two-dimensional nucleation and for crystal growth.

Cation-limited kinetic model for microbial extracellular electron transport via an outer membrane cytochrome C complex

PubMed Central

Okamoto, Akihiro; Tokunou, Yoshihide; Saito, Junki

2016-01-01

Outer-membrane c-type cytochrome (OM c-Cyt) complexes in several genera of iron-reducing bacteria, such as Shewanella and Geobacter, are capable of transporting electrons from the cell interior to extracellular solids as a terminal step of anaerobic respiration. The kinetics of this electron transport has implications for controlling the rate of microbial electron transport during bioenergy or biochemical production, iron corrosion, and natural mineral cycling. Herein, we review the findings from in-vivo and in-vitro studies examining electron transport kinetics through single OM c-Cyt complexes in Shewanella oneidensis MR-1. In-vitro electron flux via a purified OM c-Cyt complex, comprised of MtrA, B, and C proteins from S. oneidensis MR-1, embedded in a proteoliposome system is reported to be 10- to 100-fold faster compared with in-vivo estimates based on measurements of electron flux per cell and OM c-Cyts density. As the proteoliposome system is estimated to have 10-fold higher cation flux via potassium channels than electrons, we speculate that the slower rate of electron-coupled cation transport across the OM is responsible for the significantly lower electron transport rate that is observed in-vivo. As most studies to date have primarily focused on the energetics or kinetics of interheme electron hopping in OM c-Cyts in this microbial electron transport mechanism, the proposed model involving cation transport provides new insight into the rate detemining step of EET, as well as the role of self-secreted flavin molecules bound to OM c-Cyt and proton management for energy conservation and production in S. oneidensis MR-1. PMID:27924259

Molecular dynamics simulation study of nanoscale passive oxide growth on Ni-Al alloy surfaces at low temperatures

NASA Astrophysics Data System (ADS)

Sankaranarayanan, Subramanian K. R. S.; Ramanathan, Shriram

2008-08-01

Oxidation kinetics of Ni-Al (100) alloy surface is investigated at low temperatures (300-600 K) and at different gas pressures using molecular dynamics (MD) simulations with dynamic charge transfer between atoms. Monte Carlo simulations employing the bond order simulation model are used to generate the surface segregated minimum energy initial alloy configurations for use in the MD simulations. In the simulated temperature-pressure-composition regime for Ni-Al alloys, we find that the oxide growth curves follow a logarithmic law beyond an initial transient regime. The oxidation rates for Ni-Al alloys were found to decrease with increasing Ni composition. Structure and dynamical correlations in the metal/oxide/gas environments are used to gain insights into the evolution and morphology of the growing oxide film. Oxidation of Ni-Al alloys is characterized by the absence of Ni-O bond formation. Oxide films formed on the various simulated metal surfaces are amorphous in nature and have a limiting thickness ranging from ˜1.7nm for pure Al to 1.1 nm for 15% Ni-Al surfaces. Oxide scale analysis indicates significant charge transfer as well as variation in the morphology and structure of the oxide film formed on pure Al and 5% Ni-Al alloy. For oxide scales thicker than 1 nm, the oxide structure in case of pure Al exhibits a mixed tetrahedral (AlO4˜37%) and octahedral (AlO6˜19%) environment, whereas the oxide scale on Ni-Al alloy surface is almost entirely composed of tetrahedral environment (AlO4˜60%) with very little AlO6 (<1%) . The oxide growth kinetic curves are fitted to Arrhenius-type plots to get an estimate of the activation energy barriers for metal oxidation. The activation energy barrier for oxidation on pure Al was found to be 0.3 eV lower than that on 5% Ni-Al surface. Atomistic observations as well as calculated dynamical correlation functions indicate a layer by layer growth on pure Al, whereas a transition from an initial island growth mode (<75ps) to a layer by layer mode (>100ps) occurs in case of 5% Ni-Al alloy. The oxide growth on both pure Al and Ni-Al alloy surfaces occurs by inward anion and outward cation diffusions. The cation diffusion in both the cases is similar, whereas the anion diffusion in case of 5% Ni-Al is 25% lower than pure Al, thereby resulting in reduced self-limiting thickness of oxide scale on the alloy surface. The simulation findings agree well with previously reported experimental observations of oxidation on Ni-Al alloy surface.

Measurement of diffusion coefficients important in modeling the absorption rate of carbon dioxide into aqueous N-methyldiethanolamine

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

Rowley, R.L.; Adams, M.E.; Marshall, T.L.

1997-03-01

Natural gas processors use amine treating processes to remove the acid gases H{sub 2}S and CO{sub 2} from gas streams. Absorption rates of gaseous CO{sub 2} into aqueous N-methyldiethanolamine (MDEA) solutions were measured in a quiescent, inverted-tube diffusiometer by monitoring the rate of pressure drop. The absorption rate was found to be insensitive to the diffusion coefficient of CO{sub 2} in solution but very sensitive to the diffusion rate of bicarbonate and protonated MDEA ions. Evidence also suggested that chemical reaction equilibrium is rapid relative to diffusion. A numerical model was developed on the basis of these observations. The modelmore » was used to regress diffusion coefficients of bicarbonate and protonated amine, which must be equivalent by electroneutrality arguments, from measured absorption rates. Complete modeling of the absorption process also required data for the diffusion coefficient of MDEA in water. These were measured using a Taylor dispersion apparatus. CO{sub 2} absorption rates and diffusion coefficients of bicarbonate and protonated MDEA were obtained at 298.2 K and 318.2 K in solutions containing 20, 35, and 50 mass % MDEA in water.« less

Submersible microbial desalination cell for simultaneous ammonia recovery and electricity production from anaerobic reactors containing high levels of ammonia.

PubMed

Zhang, Yifeng; Angelidaki, Irini

2015-02-01

High ammonia concentration in anaerobic reactors can seriously inhibit the anaerobic digestion process. In this study, a submersible microbial desalination cell (SMDC) was developed as an innovative method to lower the ammonia level in a continuous stirred tank reactor (CSTR) by in situ ammonia recovery and electricity production. In batch experiment, the ammonia concentration in the CSTR decreased from 6 to 0.7 g-N/L during 30 days, resulting in an average recovery rate of 80 g-N/m(2)/d. Meanwhile, a maximum power density of 0.71±0.5 W/m(2) was generated at 2.85 A/m(2). Both current driven NH4(+) migration and free NH3 diffusion were identified as the mechanisms responsible for the ammonia transportation. With an increase in initial ammonia concentration and a decrease in external resistance, the SMDC performance was enhanced. In addition, the coexistence of other cations in CSTR or cathode had no negative effect on the ammonia transportation. Copyright © 2014 Elsevier Ltd. All rights reserved.

The role of ionic liquid electrolyte in an aluminum–graphite electrochemical cell

DOE PAGES

Agiorgousis, Michael L.; Sun, Yi -Yang; Zhang, Shengbai

2017-02-17

Using first-principles calculations and molecular dynamics simulation, we study the working mechanism in an aluminum–graphite electrochemical cell, which was recently reported to exhibit attractive performance. We exclude the possibility of Al 3+ cation intercalation into graphite as in standard Li-ion batteries. Instead, we show that the AlCl 4 – anion intercalation mechanism is thermodynamically feasible. By including the ionic liquid electrolyte in the overall redox reaction, we are able to reproduce the high voltage observed in experiment. The active involvement of electrolyte in the reaction suggests that the evaluation of energy density needs to take the electrolyte into consideration. Here,more » our proposed structural model is consistent with the new peaks appearing in X-ray diffraction from the intercalation compound. The high rate capability is explained by the ultralow diffusion barriers of the AlCl 4 intercalant. With the clarified working mechanism, it becomes clear that the high voltage of the Al–graphite cell is a result of the thermodynamic instability of the AlCl 4-intercalated graphite.« less

Electrical characteristics in reverse electrodialysis using nanoporous membranes

NASA Astrophysics Data System (ADS)

Chanda, Sourayon; Tsai, Peichun Amy

2017-11-01

We experimentally and numerically investigate the effects of concentration difference and flow velocity on sustainable electricity generation and associated fluid dynamics using a single reverse electrodialysis (RED) cell. By exploiting the charge-selective nature of nanoporous interfaces, electrical energy is generated by reverse electrodialysis harnessing chemical Gibbs energy via a salinity gradient. Experimentally, a RED cell was designed with two reservoirs, which are separated by a nanoporous, cation-selective membrane. We injected deionized water through one reservoir, whereas a solution of high salt concentration through the other. The gradient of salt concentration primarily drives the flow in the charged nano-pores, due to the interplay between charge selectivity, diffusion processes, and electro-migration. The current-voltage characteristics of the single RED cell shows a linear current-voltage relationship, similar to an electrochemical cell. The membrane resistance is increased with increasing salt concentration difference and external flow rate. The present experimental work was further analyzed numerically to better understand the detailed electrical and flow fields under different concentration gradients and external flows. NSERC Discovery, Accelerator, and CRC Programs.

Urea-based hydrothermal synthesis of LiNi0.5Co0.2Mn0.3O2 cathode material for Li-ion battery

NASA Astrophysics Data System (ADS)

Shi, Yang; Zhang, Minghao; Fang, Chengcheng; Meng, Ying Shirley

2018-08-01

A urea-based hydrothermal approach has been applied to synthesize LiNi0.5Co0.2Mn0.3O2 (NCM523) cathode materials with focus on investigating the influence of the reaction conditions on their electrochemical performance. The compositions of the carbonate precursor are precisely controlled by tuning urea concentration, hydrothermal reaction temperature, and time. The mole ratio between urea and transition metal ions and reaction temperature influence the composition of the precursor; while the reaction time influences the electrochemical performance of the final product. The optimized materials show better cyclability and rate capability compared with the materials synthesized with other hydrothermal reaction conditions. The enhancement is attributed to the larger Li+ diffusion coefficient and lower charge transfer resistance, which are due to the lower degree of Li/Ni cation mixing and more uniform distribution of transition metal ions. This work is a systematic study on the synthesis of NCM523 cathode material by a urea-based hydrothermal approach.

Structural Characterization of Unsaturated Phosphatidylcholines Using Traveling Wave Ion Mobility Spectrometry

PubMed Central

Kim, Hugh I.; Kim, Hyungjun; Pang, Eric S.; Ryu, Ernest K.; Beegle, Luther W.; Loo, Joseph A.; Goddard, William A.; Kanik, Isik

2009-01-01

A number of phosphatidylcholine (PC) cations spanning a mass range of 400 to 1000 Da are investigated using electrospray ionization mass spectrometry coupled with traveling wave ion mobility spectrometry (TWIMS). A high correlation between mass and mobility is demonstrated with saturated phosphatidylcholine cations in N2. A significant deviation from this mass-mobility correlation line is observed for the unsaturated PC cation. We found that the double bond in the acyl chain causes a 5% reduction in drift time. The drift time is reduced at a rate of ~1% for each additional double bond. Theoretical collision cross sections of PC cations exhibit good agreement with experimentally evaluated values. Collision cross sections are determined using the recently derived relationship between mobility and drift time in TWIMS stacked ring ion guide (SRIG) and compared to estimate collision cross-sections using empiric calibration method. Computational analysis was performed using the modified trajectory (TJ) method with nonspherical N2 molecules as the drift gas. The difference between estimated collision cross-sections and theoretical collision cross-sections of PC cations is related to the sensitivity of the PC cation collision cross-sections to the details of the ion-neutral interactions. The origin of the observed correlation and deviation between mass and mobility of PC cations is discussed in terms of the structural rigidity of these molecules using molecular dynamic simulations. PMID:19764704

Diel plant water use and competitive soil cation exchange interact to enhance NH 4 + and K + availability in the rhizosphere

DOE PAGES

Espeleta, Javier F.; Cardon, Zoe G.; Mayer, K. Ulrich; ...

2016-11-12

Hydro-biogeochemical processes in the rhizosphere regulate nutrient and water availability, and thus ecosystem productivity. We hypothesized that two such processes often neglected in rhizosphere models — diel plant water use and competitive cation exchange — could interact to enhance availability of K + and NH 4 +, both high-demand nutrients. A rhizosphere model with competitive cation exchange was used to investigate how diel plant water use (i.e., daytime transpiration coupled with no nighttime water use, with nighttime root water release, and with nighttime transpiration) affects competitive ion interactions and availability of K + and NH 4 +. Competitive cation exchangemore » enabled lowdemand cations that accumulate against roots (Ca 2+, Mg 2+, Na +) to desorb NH 4 + and K + from soil, generating non-monotonic dissolved concentration profiles (i.e. ‘hotspots’ 0.1–1 cm from the root). Cation accumulation and competitive desorption increased with net root water uptake. Daytime transpiration rate controlled diel variation in NH 4 + and K + aqueous mass, nighttime water use controlled spatial locations of ‘hotspots’, and day-to-night differences in water use controlled diel differences in ‘hotspot’ concentrations. Finally, diel plant water use and competitive cation exchange enhanced NH 4 + and K + availability and influenced rhizosphere concentration dynamics. Demonstrated responses have implications for understanding rhizosphere nutrient cycling and plant nutrient uptake.« less

Particle transport through hydrogels is charge asymmetric.

PubMed

Zhang, Xiaolu; Hansing, Johann; Netz, Roland R; DeRouchey, Jason E

2015-02-03

Transport processes within biological polymer networks, including mucus and the extracellular matrix, play an important role in the human body, where they serve as a filter for the exchange of molecules and nanoparticles. Such polymer networks are complex and heterogeneous hydrogel environments that regulate diffusive processes through finely tuned particle-network interactions. In this work, we present experimental and theoretical studies to examine the role of electrostatics on the basic mechanisms governing the diffusion of charged probe molecules inside model polymer networks. Translational diffusion coefficients are determined by fluorescence correlation spectroscopy measurements for probe molecules in uncharged as well as cationic and anionic polymer solutions. We show that particle transport in the charged hydrogels is highly asymmetric, with diffusion slowed down much more by electrostatic attraction than by repulsion, and that the filtering capability of the gel is sensitive to the solution ionic strength. Brownian dynamics simulations of a simple model are used to examine key parameters, including interaction strength and interaction range within the model networks. Simulations, which are in quantitative agreement with our experiments, reveal the charge asymmetry to be due to the sticking of particles at the vertices of the oppositely charged polymer networks. Copyright © 2015 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Direct measurement of concentration distribution within the boundary layer of an ion-exchange membrane.

PubMed

Choi, Jae-Hwan; Park, Jin-Soo; Moon, Seung-Hyeon

2002-07-15

In this study the concentration distributions within the diffusion boundary layer were obtained by directly measuring the potential drops while the currents (under- and overlimiting) passed through the Neosepta CMX cation-exchange membrane (Tokuyama Corp., Japan). Potential drops according to the distance from the membrane surface on the depleted side were measured using a microelectrode to obtain the concentration profile. From the concentration profiles obtained, it was observed that the diffusion boundary layers existed in the range of 300-350 microm, which reasonably coincide with the theoretical diffusion boundary layer thickness calculated from the limiting current density. Although there were some deviations between the concentrations determined from the Nernst model and those from experiments, it was confirmed that the Nernst model effectively depicts the transport phenomena in the ion-exchange membrane system. In addition it was found that the salt concentration at the membrane surface increased when the currents applied exceeded the limiting current. It is thought that the concentration polarization formed in the diffusion boundary layer at currents near or lower than the limiting current was disturbed by a turbulent convection when the current was greater than the limiting current. As a consequence, the concentration at the membrane surface increased to a sufficient level for generation of the overlimiting current.

Movement of Cations through Cuticles of Citrus aurantium and Acer saccharum1

PubMed Central

Tyree, Melvin T.; Tabor, Christopher A.; Wescott, Charles R.

1990-01-01

We examined some biophysical mechanisms of ion migration across leaf cuticles enzymatically isolated from Acer saccharum L. and Citrus aurantium L. leaves. Diffusion potential measurements were used to calculate the permeabilities of Cl-, Li+, Na+, and Cs+ ions all as a ratio with respect to the permeability of K+ in cuticles. In 2 millimolar ionic strength solutions the permeability sequence from high to low was K = Cs > Na > Li » Cl. When the outer and inner surfaces of cuticles were bathed in artificial precipitation and artificial apoplast, respectively, diffusion potentials ranging from −52 to −91 millivolts were measured (inside negative). The Goldman equation predicted that the measured potentials were enough to increase the driving force on the accumulation of heavy metals by a factor of 4 to 7. Other ions migrate with forces 3 to 10 times less than predicted by the Goldman equation for concentration differences alone. Our analysis showed that Ca2+, and perhaps Mg2+, might even be accumulated against concentration gradients under some circumstances. Their uptake was apparently driven by the diffusion potentials created by the outward migration of monovalent salts. We feel that future models predicting leaching of nutrients from trees during acid rain events must be modified to account for the probable influence of diffusion potentials on ion migration. PMID:16667677

Dynamic adsorption of CO2/N2 on cation-exchanged chabazite SSZ-13: A breakthrough analysis

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

Bower, Jamey K.; Barpaga, Dushyant; Prodinger, Sebastian

2018-04-17

Alkali exchanged SSZ-13 adsorbents were investigated for their applicability in separating N2 from CO2 in flue gas streams using a dynamic breakthrough method. In contrast to IAST calculations based on equilibrium isotherms, K+ exchanged SSZ-13 was found to yield the best N2 productivity under dynamic conditions where diffusion properties play a significant role. This was attributed to the selective, partial blockage of access to the CHA cavities enhancing the separation potential in a 15/85 CO2/N2 binary gas mixture.

Dynamic Adsorption of CO 2 /N 2 on Cation-Exchanged Chabazite SSZ-13: A Breakthrough Analysis

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

Bower, Jamey K.; Barpaga, Dushyant; Prodinger, Sebastian

2018-03-30

Alkali exchanged SSZ-13 adsorbents were investigated for their applicability in separating N2 from CO 2 in flue gas streams using a dynamic breakthrough method. In contrast to IAST calculations based on equilibrium isotherms, K+ exchanged SSZ-13 was found to yield the best N2 productivity under dynamic conditions where diffusion properties play a significant role. This was attributed to the selective, partial blockage of access to the CHA cavities enhancing the separation potential in a 15/85 CO2/N2 binary gas mixture.

Transactions of the Conference of Army Mathematicians (21st) Held at White Sands Missile Range, N. Mex. on 14-16 May 1975

DTIC Science & Technology

1976-02-01

A. Hussain and S. L. Pu . . . . . . . . . . . . . 81 Development and Application of Dynamic r~athematical Models for Evaluation of Military Systems ...Reacting Diffusive Systems Donald S. Cohen ......•.......••..• A New Numerical Method of Solution of Schrodinger’s Equation George Morales and Robert G...Eisenhower Avenue Alexandria. Virginia 22304 DEVELOPMENT AND APPLI CATION OF DYNA~lI C r·1ATHH1ATI CAL MODELS FOR EVALUATION OF MILITARY SYSTEMS , FORCES

Cation–hydroxide–water coadsorption inhibits the alkaline hydrogen oxidation reaction

DOE PAGES

Chung, Hoon Taek; Martinez, Ulises; Matanovic, Ivana; ...

2016-10-24

Rotating disk electrode voltammograms and infrared reflection absorption spectra indicate that the hydrogen oxidation reaction of platinum in 0.1 M tetramethylammonium hydroxide solution is adversely impacted by time-dependent and potential-driven cation–hydroxide–water coadsorption. Impedance analysis suggests that the hydrogen oxidation reaction inhibition is mainly caused by the hydrogen diffusion barrier of the coadsorbed trilayer rather than intuitive catalyst site blocking by the adsorbed cation species. Finally, these results give useful insights on how to design ionomeric binders for advanced alkaline membrane fuel cells.

Influence of Biochar on Deposition and Release of Clay Colloids in Saturated Porous Media.

PubMed

Haque, Muhammad Emdadul; Shen, Chongyang; Li, Tiantian; Chu, Haoxue; Wang, Hong; Li, Zhen; Huang, Yuanfang

2017-11-01

Although the potential application of biochar in soil remediation has been recognized, the effect of biochar on the transport of clay colloids, and accordingly the fate of colloid-associated contaminants, is unclear to date. This study conducted saturated column experiments to systematically examine transport of clay colloids in biochar-amended sand porous media in different electrolytes at different ionic strengths. The obtained breakthrough curves were simulated by the convection-diffusion equation, which included a first-order deposition and release terms. The deposition mechanisms were interpreted by calculating Derjaguin-Landau-Verwey-Overbeek interaction energies. A linear relationship between the simulated deposition rate or the attachment efficiency and the fraction of biochar was observed ( ≥ 0.91), indicating more favorable deposition in biochar than in sand. The interaction energy calculations show that the greater deposition in biochar occurs because the half-tube-like cavities on the biochar surfaces favor deposition in secondary minima and the nanoscale physical and chemical heterogeneities on the biochar surfaces increase deposition in primary minima. The deposited clay colloids in NaCl can be released by reduction of ionic strength, whereas the presence of a bivalent cation (Ca) results in irreversible deposition due to the formation of cation bridging between the colloids and biochar surfaces. The deposition and release of clay colloids on or from biochar surfaces not only change their mobilizations in the soil but also influence the efficiency of the biochar for removal of pollutants. Therefore, the influence of biochar on clay colloid transport must be considered before application of the biochar in soil remediation. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Construction of Uranyl Selective Electrode Based on Complex of Uranyl Ion with New Ligand Carboxybenzotriazole in PVC Matrix Membrane

NASA Astrophysics Data System (ADS)

Abu-Dalo, M. A.; Al-Rawashdeh, N. A. F.; Al-Mheidat, I. R.; Nassory, N. S.

2015-10-01

In the present study uranyl selective electrodes in polyvinyl chloride (PVC) matrix membrane were prepared based on a complex of uranyl ion (UO2) with carboxybenzotriazole (CBT) as ligand. The effect of the nature of plasticizer in PVC matrix were evaluated using three different plasticizers, these are dibutyl phthalate (DBP), dioctyl phthalate (DOP) and bis(2-ethylhexyl) sebacate (BHS). The results of this study indicated that the best plasticizer could be used is the DBP, which may be attributed to its lowest viscosity value compared to DOP and BHS. The electrodes with DBP as plasticizer exhibits a Nernstian response with a slope of 28.0 mV/ decade, over a wide range of concentration from 3.0×10-5-6.0×10-2 M and a detection limit of 4.0×10-6 M. It can be used in the pH range of 4.0-10.0 with a response time of less than 10 s for DBP and 25 s for both DOP and BHS. The effects of ions interferences on the electrode response were evaluated. The di- and tri-valent cations were found to interfere less than univalent cations, which was attributed to the high diffusion and the exchange rate between the univalent ions and the uranyl ion solution. The electrodes were characterized by Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron microscopy (SEM). The results of the standard addition method were satisfactory with errors less than 7%. The developed electrode was found to be fast, sensitive and reliable indicated its potential use in measuring the uranly ion concentration in the field.

Molecular Recognition and Structural Influences on Function in Bio-nanosystems of Nucleic Acids and Proteins

NASA Astrophysics Data System (ADS)

Sethaphong, Latsavongsakda

This work examines smart material properties of rational self-assembly and molecular recognition found in nano-biosystems. Exploiting the sequence and structural information encoded within nucleic acids and proteins will permit programmed synthesis of nanomaterials and help create molecular machines that may carry out new roles involving chemical catalysis and bioenergy. Responsive to different ionic environments thru self-reorgnization, nucleic acids (NA) are nature's signature smart material; organisms such as viruses and bacteria use features of NAs to react to their environment and orchestrate their lifecycle. Furthermore, nucleic acid systems (both RNA and DNA) are currently exploited as scaffolds; recent applications have been showcased to build bioelectronics and biotemplated nanostructures via directed assembly of multidimensional nanoelectronic devices 1. Since the most stable and rudimentary structure of nucleic acids is the helical duplex, these were modeled in order to examine the influence of the microenvironment, sequence, and cation-dependent perturbations of their canonical forms. Due to their negatively charged phosphate backbone, NA's rely on counterions to overcome the inherent repulsive forces that arise from the assembly of two complementary strands. As a realistic model system, we chose the HIV-TAR helix (PDB ID: 397D) to study specific sequence motifs on cation sequestration. At physiologically relevant concentrations of sodium and potassium ions, we observed sequence based effects where purine stretches were adept in retaining high residency cations. The transitional space between adenine and guanosine nucleotides (ApG step) in a sequence proved the most favorable. This work was the first to directly show these subtle interactions of sequence based cationic sequestration and may be useful for controlling metallization of nucleic acids in conductive nanowires. Extending the study further, we explored the degree to which the structure of NA duplexes alone interacted with cations distinct from a specific sequence. Under physiologically relevant conditions, a duplex of RNA polyguanine-polycitidine was highly responsive and able to sequester cations to the middle of the purine stretches. The least responsive structure was a DNA polyadenine-polythymine duplex. A random sequence DNA duplex contorted into an RNA-like helix resulted in cationic dynamics similar to RNA systems. These studies showed that cation diffusive binding events in nucleic acid duplex structures are sequence specific and heavily influenced by structural aspects helical forms to account for much of the differences observed. Although structural information in nucleic acids is encoded within their sequence, linking amino acid sequence to protein structure is murkier; the structural information within proteins is encoded by the folding process itself: a complex phenomenon driven toward the equilibrium state of the active conformation. Upwards of two thirds of a protein's sequence can be substituted with similar amino acids without significantly perturbing its function; conserved residues of about 10% seem to be vital; since evolutionary selection pressure in proteins operates 3-dimenionally, a linear sequence is partially informative. We explored this problem by folding de-novo the cytosolic portion of the membrane protein, cellulose synthase, CESA1 from upland cotton, Gossypium hirsutum (Ghcesa1). The cytoplasmic region was generated by homology modeling and refined with molecular dynamics. These mutations impair local structural flexibility which likely results in cellulose that is produced at a lower rate and is less crystalline. Additional modeling of fragments of cellulose synthases from the model plant, Arabidopsis thaliana, offered novel insights into the function of conserved cytosolic domains within plant cellulose synthases. Transport mechanisms related to the transmembrane region revealed significant differences between plants and a bacterial complex. These studies generated possible mutations that may allow for the creation of new synthases and identified other avenues of research in order to develop technologies that may alter the crystallinity and other useful properties of cellulose. 1. Karplus, K., SAM-T08, HMM-based protein structure prediction. Nucleic Acids Research, 2009. 37: p. W492-W497.

Intramolecular Electron Transfer in Bis(tetraalkyl Hydrazine) and Bis(hydrazyl) Radical Cations.

NASA Astrophysics Data System (ADS)

Chang, Hao

A series of multicyclic bis(hydrazine) and bis(diazenium) compounds connected by relatively rigid hydrocarbon frameworks were prepared for the study of intramolecular electron transfer. The thermodynamics of electron removal of these compounds was investigated by cyclic voltammetry. The difference between the first and second oxidation potentials for the 4 sigma-bonded species was found to be larger for the bis(hydrazyl) radical systems than for the bis(hydrazines) by ca. 0.2 V (4.6 kcal/mol). This indicates a greater degree of interaction between the two nitrogen moieties for the hydrazyl systems, which is consistent with a greater degree of electronic coupling (H _{rm AB}) in these systems. The ESR spectra of the 4 sigma -bonded bis(hydrazine) radical cations indicate localized radical cations, which corresponds to slow intramolecular electron transfer on the ESR timescale. Conversely, the ESR spectra of the corresponding bis(hydrazyl) radical cation systems show nitrogen hyperfine splittings of a(4N) of ca. 4.5 G. This indicates that intramolecular electron transfer between the two nitrogen moieties is fast on the ESR timescale; the rate of exchange, k_ {rm ex} was estimated to be well above 1.9 times 10^8 s^{-1}. The contrast in exchange rates is consistent with the large geometry change upon oxidation which is characteristic of hydrazines. The hydrazyls undergo a smaller geometry change upon oxidation, and thus are expected to exhibit smaller inner-sphere reorganization energies. The optical spectra of these radical species was investigated in hopes of observing absorption bands corresponding to intramolecular electron transfer, as predicted by Hush theory. A broad absorption band was observed in the near IR region for the saturated bis(hydrazyl) radical cation system at 1060 nm (9420 cm^{-1} ) in acetonitrile at room temperature, and was accompanied by a narrower band at 1430 nm (6993 cm^ {-1}). The width of this band was estimated to be 545 nm (6496 cm^{-1}). A much higher energy band was observed in the UV/Vis region, at 520 nm (19,230 cm^{-1}) in acetonitrile for the corresponding bis(hydrazine) radical cation. The width of this band was estimated to be 240 nm (7211 cm^{-1}). The difference in the energies of these absorbance bands, E _{rm op}, reflects the different inner-sphere reorganization energies of the hydrazyl and hydrazine systems. Using Hush analysis, the electron coupling, H_{rm AB} , was calculated to be ca. 3.5 kcal/mol for the bis(hydrazyl) radical cation systems; a smaller value of H_{rm AB} of 1 kcal/mol was obtained for the bis(hydrazine) radical cations. This difference in electronic coupling is consistent with the faster rate of electron transfer, as well as the smaller inner-sphere reorganization energy in the bis(hydrazyl) systems.

Simultaneous Extraction of Lithium and Hydrogen from Seawater

DTIC Science & Technology

2011-01-26

ion chromatography . Anions were analyzed by Anion Ion Chromatography (Instrument Dionex ...Cation Ion Chromatography (Instrument Dionex DX-500, Cation Column Dionex CS12A; CG12A Guard, eluent: 20.00 mM methanesulfonic acid, flow rate:1.25...for 2 hours and sprayed (P=6psig) with an air-sprayer on Nafion. The dimension of sprayed area is 1˝ x 1˝. Ion Chromatography (IC): Ions

Removal of lead, cadmium, zinc, and copper from industrial wastewater by carbon developed from walnut, hazelnut, almond, pistachio shell, and apricot stone.

PubMed

Kazemipour, Maryam; Ansari, Mehdi; Tajrobehkar, Shabnam; Majdzadeh, Majdeh; Kermani, Hamed Reihani

2008-01-31

In this work, adsorption of copper (Cu), zinc (Zn), lead (Pb), and cadmium (Cd) that exist in industrial wastewater onto the carbon produced from nutshells of walnut, hazelnut, pistachio, almond, and apricot stone has been investigated. All the agricultural shell or stone used were ground, sieved to a defined size range, and carbonized in an oven. Time and temperature of heating were optimized at 15 min and 800 degrees C, respectively, to reach maximum removal efficiency. Removal efficiency was optimized regarding to the initial pH, flow rate, and dose of adsorbent. The maximum removal occurred at pH 6-10, flow rate of 3 mL/min, and 0.1g of the adsorbent. Capacity of carbon sources for removing cations will be considerably decreased in the following times of passing through them. Results showed that the cations studied significantly can be removed by the carbon sources. Efficiency of carbon to remove the cations from real wastewater produced by copper industries was also studied. Finding showed that not only these cations can be removed considerably by the carbon sources noted above, but also removing efficiency are much more in the real samples. These results were in adoption to those obtained by standard mixture synthetic wastewater.

Kinetic determinations of accurate relative oxidation potentials of amines with reactive radical cations.

PubMed

Gould, Ian R; Wosinska, Zofia M; Farid, Samir

2006-01-01

Accurate oxidation potentials for organic compounds are critical for the evaluation of thermodynamic and kinetic properties of their radical cations. Except when using a specialized apparatus, electrochemical oxidation of molecules with reactive radical cations is usually an irreversible process, providing peak potentials, E(p), rather than thermodynamically meaningful oxidation potentials, E(ox). In a previous study on amines with radical cations that underwent rapid decarboxylation, we estimated E(ox) by correcting the E(p) from cyclic voltammetry with rate constants for decarboxylation obtained using laser flash photolysis. Here we use redox equilibration experiments to determine accurate relative oxidation potentials for the same amines. We also describe an extension of these experiments to show how relative oxidation potentials can be obtained in the absence of equilibrium, from a complete kinetic analysis of the reversible redox kinetics. The results provide support for the previous cyclic voltammetry/laser flash photolysis method for determining oxidation potentials.

Mapping trace element distribution in fossil teeth and bone with LA-ICP-MS

NASA Astrophysics Data System (ADS)

Hinz, E. A.; Kohn, M. J.

2009-12-01

Trace element profiles were measured in fossil bones and teeth from the late Pleistocene (c. 25 ka) Merrell locality, Montana, USA, by using laser-ablation ICP-MS. Laser-ablation ICP-MS can collect element counts along predefined tracks on a sample’s surface using a constant ablation speed allowing for rapid spatial sampling of element distribution. Key elements analyzed included common divalent cations (e.g. Sr, Zn, Ba), a suite of REE (La, Ce, Nd, Sm, Eu, Yb), and U, in addition to Ca for composition normalization and standardization. In teeth, characteristic diffusion penetration distances for all trace elements are at least a factor of 4 greater in traverses parallel to the dentine-enamel interface (parallel to the growth axis of the tooth) than perpendicular to the interface. Multiple parallel traverses in sections parallel and perpendicular to the tooth growth axis were transformed into trace element maps, and illustrate greater uptake of all trace elements along the central axis of dentine compared to areas closer to enamel, or within the enamel itself. Traverses in bone extending from the external surface, through the thickness of cortical bone and several mm into trabecular bone show major differences in trace element uptake compared to teeth: U and Sr are homogeneous, whereas all REE show a kinked profile with high concentrations on outer surfaces that decrease by several orders of magnitude within a few mm inward. The Eu anomaly increases uniformly from the outer edge of bone inward, whereas the Ce anomaly decreases slightly. These observations point to major structural anisotropies in trace element transport and uptake during fossilization, yet transport and uptake of U and REE are not resolvably different. In contrast, transport and uptake of U in bone must proceed orders of magnitude faster than REE as U is homogeneous whereas REE exhibit strong gradients. The kinked REE profiles in bone unequivocally indicate differential transport rates, consistent with a double-medium diffusion model in which microdomains with slow diffusivities are bounded by fast-diffusing pathways.

The role of intra-NAPL diffusion on mass transfer from MGP residuals

NASA Astrophysics Data System (ADS)

Shafieiyoun, Saeid; Thomson, Neil R.

2018-06-01

An experimental and computational study was performed to investigate the role of multi-component intra-NAPL diffusion on NAPL-water mass transfer. Molecular weight and the NAPL component concentrations were determined to be the most important parameters affecting intra-NAPL diffusion coefficients. Four NAPLs with different viscosities but the same quantified mass were simulated. For a spherical NAPL body, a combination of NAPL properties and interphase mass transfer rate can result in internal diffusion limitations. When the main intra-NAPL diffusion coefficients are in the range of self-diffusion coefficients (10-5 to 10-6 cm2/s), dissolution is not limited by internal diffusion except for high mass transfer rate coefficients (>180 cm/day). For a complex and relatively high viscous NAPL (>50 g/(cm s)), smaller intra-NAPL diffusion coefficients (<10-8) are expected and even low mass transfer rate coefficients ( 6 cm/day) can result in diffusion-limited dissolution.

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

USGS Publications Warehouse

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

2004-01-01

Manganese oxides are important scavengers of trace metals and other contaminants in the environment. The inclusion of Mn oxides in predictive models, however, has been difficult due to the lack of a comprehensive set of sorption reactions consistent with a given surface complexation model (SCM), and the discrepancies between published sorption data and predictions using the available models. The authors have compiled a set of surface complexation reactions for synthetic hydrous Mn oxide (HMO) using a two surface site model and the diffuse double layer SCM which complements databases developed for hydrous Fe (III) oxide, goethite and crystalline Al oxide. This compilation encompasses a range of data observed in the literature for the complex HMO surface and provides an error envelope for predictions not well defined by fitting parameters for single or limited data sets. Data describing surface characteristics and cation sorption were compiled from the literature for the synthetic HMO phases birnessite, vernadite and ??-MnO2. A specific surface area of 746 m2g-1 and a surface site density of 2.1 mmol g-1 were determined from crystallographic data and considered fixed parameters in the model. Potentiometric titration data sets were adjusted to a pH1EP value of 2.2. Two site types (???XOH and ???YOH) were used. The fraction of total sites attributed to ???XOH (??) and pKa2 were optimized for each of 7 published potentiometric titration data sets using the computer program FITEQL3.2. pKa2 values of 2.35??0.077 (???XOH) and 6.06??0.040 (???YOH) were determined at the 95% confidence level. The calculated average ?? value was 0.64, with high and low values ranging from 1.0 to 0.24, respectively. pKa2 and ?? values and published cation sorption data were used subsequently to determine equilibrium surface complexation constants for Ba2+, Ca2+, Cd 2+, Co2+, Cu2+, Mg2+, Mn 2+, Ni2+, Pb2+, Sr2+ and Zn 2+. In addition, average model parameters were used to predict additional sorption data for which complementary titration data were not available. The two-site model accounts for variability in the titration data and most metal sorption data are fit well using the pKa2 and ?? values reported above. A linear free energy relationship (LFER) appears to exist for some of the metals; however, redox and cation exchange reactions may limit the prediction of surface complexation constants for additional metals using the LFER. ?? 2003 Elsevier Ltd. All rights reserved.

Engineering Fast Ion Conduction and Selective Cation Channels for a High-Rate and High-Voltage Hybrid Aqueous Battery.

PubMed

Liu, Chunyi; Wang, Xusheng; Deng, Wenjun; Li, Chang; Chen, Jitao; Xue, Mianqi; Li, Rui; Pan, Feng

2018-03-14

The rechargeable aqueous metal-ion battery (RAMB) has attracted considerable attention due to its safety, low costs, and environmental friendliness. Yet the poor-performance electrode materials lead to a low feasibility of practical application. A hybrid aqueous battery (HAB) built from electrode materials with selective cation channels could increase the electrode applicability and thus enlarge the application of RAMB. Herein, we construct a high-voltage K-Na HAB based on K 2 FeFe(CN) 6 cathode and carbon-coated NaTi 2 (PO 4 ) 3 (NTP/C) anode. Due to the unique cation selectivity of both materials and ultrafast ion conduction of NTP/C, the hybrid battery delivers a high capacity of 160 mAh g -1 at a 0.5 C rate. Considerable capacity retention of 94.3 % is also obtained after 1000 cycles at even 60 C rate. Meanwhile, high energy density of 69.6 Wh kg -1 based on the total mass of active electrode materials is obtained, which is comparable and even superior to that of the lead acid, Ni/Cd, and Ni/MH batteries. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nature of electron trap states under inversion at In0.53Ga0.47As/Al2O3 interfaces

NASA Astrophysics Data System (ADS)

Colleoni, Davide; Pourtois, Geoffrey; Pasquarello, Alfredo

2017-03-01

In and Ga impurities substitutional to Al in the oxide layer resulting from diffusion out of the substrate are identified as candidates for electron traps under inversion at In0.53Ga0.47As/Al2O3 interfaces. Through density-functional calculations, these defects are found to be thermodynamically stable in amorphous Al2O3 and to be able to capture two electrons in a dangling bond upon breaking bonds with neighboring O atoms. Through a band alignment based on hybrid functional calculations, it is inferred that the corresponding defect levels lie at ˜1 eV above the conduction band minimum of In0.53Ga0.47As, in agreement with measured defect densities. These results support the technological importance of avoiding cation diffusion into the oxide layer.