Electrospray droplet exposure to organic vapors: metal ion removal from proteins and protein complexes.

Science.gov (United States)

DeMuth, J Corinne; McLuckey, Scott A

2015-01-20

The exposure of aqueous nanoelectrospray droplets to various organic vapors can dramatically reduce sodium adduction on protein ions in positive ion mass spectra. Volatile alcohols, such as methanol, ethanol, and isopropanol lead to a significant reduction in sodium ion adduction but are not as effective as acetonitrile, acetone, and ethyl acetate. Organic vapor exposure in the negative ion mode, on the other hand, has essentially no effect on alkali ion adduction. Evidence is presented to suggest that the mechanism by which organic vapor exposure reduces alkali ion adduction in the positive mode involves the depletion of alkali metal ions via ion evaporation of metal ions solvated with organic molecules. The early generation of metal/organic cluster ions during the droplet desolvation process results in fewer metal ions available to condense on the protein ions formed via the charged residue mechanism. These effects are demonstrated with holomyoglobin ions to illustrate that the metal ion reduction takes place without detectable protein denaturation, which might be revealed by heme loss or an increase in charge state distribution. No evidence is observed for denaturation with exposure to any of the organic vapors evaluated in this work.

Solvation and Ion Pair Association in Aqueous Metal Sulfates: Interpretation of NDIS raw data by isobaric-isothermal molecular dynamics simulation

International Nuclear Information System (INIS)

Chialvo, Ariel A.; Simonson, J. Michael

2010-01-01

We analyzed the solvation behavior of aqueous lithium, nickel, and ytterbium sulfates at ambient conditions in terms of the relevant radial distributions functions and the corresponding first-order difference of the sulfur-site neutron weighted distribution functions generated by isothermal-isobaric molecular dynamics simulation. We determined of the partial contributions to the neutron weighted distribution functions, to identify the main peaks, and the effect of the contact ion-pair configuration on the resulting H-S coordination number. Finally, we assessed the extent of the ion-pair formation according to Poirier-DeLap formalism and highlighted the significant increase of the ion-pair association exhibited by these salts with cation charge.

Wave–particle interactions in a resonant system of photons and ion-solvated water

Energy Technology Data Exchange (ETDEWEB)

Konishi, Eiji, E-mail: konishi.eiji.27c@st.kyoto-u.ac.jp

2017-02-26

Highlights: • We consider a QED model of rotating water molecules with ion solvation effects. • The equations of motion are cast in terms of a conventional free electron laser. • We offer a new quantum coherence mechanism induced by collective instability. - Abstract: We investigate a laser model for a resonant system of photons and ion cluster-solvated rotating water molecules in which ions in the cluster are identical and have very low, non-relativistic velocities and direction of motion parallel to a static electric field induced in a single direction. This model combines Dicke superradiation with wave–particle interaction. As the result, we find that the equations of motion of the system are expressed in terms of a conventional free electron laser system. This result leads to a mechanism for dynamical coherence, induced by collective instability in the wave–particle interaction.

Mode coupling theory analysis of electrolyte solutions: Time dependent diffusion, intermediate scattering function, and ion solvation dynamics.

Science.gov (United States)

Roy, Susmita; Yashonath, Subramanian; Bagchi, Biman

2015-03-28

A self-consistent mode coupling theory (MCT) with microscopic inputs of equilibrium pair correlation functions is developed to analyze electrolyte dynamics. We apply the theory to calculate concentration dependence of (i) time dependent ion diffusion, (ii) intermediate scattering function of the constituent ions, and (iii) ion solvation dynamics in electrolyte solution. Brownian dynamics with implicit water molecules and molecular dynamics method with explicit water are used to check the theoretical predictions. The time dependence of ionic self-diffusion coefficient and the corresponding intermediate scattering function evaluated from our MCT approach show quantitative agreement with early experimental and present Brownian dynamic simulation results. With increasing concentration, the dispersion of electrolyte friction is found to occur at increasingly higher frequency, due to the faster relaxation of the ion atmosphere. The wave number dependence of intermediate scattering function, F(k, t), exhibits markedly different relaxation dynamics at different length scales. At small wave numbers, we find the emergence of a step-like relaxation, indicating the presence of both fast and slow time scales in the system. Such behavior allows an intriguing analogy with temperature dependent relaxation dynamics of supercooled liquids. We find that solvation dynamics of a tagged ion exhibits a power law decay at long times-the decay can also be fitted to a stretched exponential form. The emergence of the power law in solvation dynamics has been tested by carrying out long Brownian dynamics simulations with varying ionic concentrations. The solvation time correlation and ion-ion intermediate scattering function indeed exhibit highly interesting, non-trivial dynamical behavior at intermediate to longer times that require further experimental and theoretical studies.

Interaction of d(10) metal ions with thioether ligands: a thermodynamic and theoretical study.

Science.gov (United States)

Melchior, Andrea; Peralta, Elena; Valiente, Manuel; Tavagnacco, Claudio; Endrizzi, Francesco; Tolazzi, Marilena

2013-05-07

Thermodynamic parameters of complex formation between d(10) metal ions, such as Zn(2+), Cd(2+), Hg(2+) and Ag(+), and the macrocyclic thioether 1,4,7-trithiacyclononane ([9]AneS3) or the monodentate diethylsulfide (Et(2)S), in acetonitrile (AN) at 298.15 K, were studied by a systematic methodology including potentiometry, calorimetry and polarography. [9]AneS3 is able to form complexes with all the target cations, Et(2)S only reacts with Hg(2+) and Ag(+). Mononuclear ML(j) (j = 1, 2) complexes are formed with all the metal ions investigated, where the affinity order is Hg(2+) > Ag(+) > Cd(2+) ≈ Zn(2+) when L = [9]AneS3 and Hg(2+) > Ag(+) when L = Et(2)S. Enthalpy and entropy values are generally negative, as a consequence of both metal ion interactions with neutral ligands, the reagents' loss of degrees of freedom and the release of solvating molecules. DFT calculations on the complexes formed with [9]AneS3 in vacuum and in AN are also carried out, to correlate experimental and theoretical thermodynamic values and to highlight the interplay between the direct metal-thioether interaction and the solvation effects. Trends obtained for the stability constants and enthalpies of the 1 : 1 and 1 : 2 complexes in solvent well reproduce the experimental ones for all the divalent metal ion complexes with [9]AneS3 and indicate the release of 3 AN molecules in the formation of each consecutive octahedral complex. In addition, calculated and experimental values for Ag(+) complex formation in solution suggest that in AgL(2) species [9]AneS3 ligands are not both tridentate.

Ion solvation in polymer blends and block copolymer melts: effects of chain length and connectivity on the reorganization of dipoles.

Science.gov (United States)

Nakamura, Issei

2014-05-29

We studied the thermodynamic properties of ion solvation in polymer blends and block copolymer melts and developed a dipolar self-consistent field theory for polymer mixtures. Our theory accounts for the chain connectivity of polymerized monomers, the compressibility of the liquid mixtures under electrostriction, the permanent and induced dipole moments of monomers, and the resultant dielectric contrast among species. In our coarse-grained model, dipoles are attached to the monomers and allowed to rotate freely in response to electrostatic fields. We demonstrate that a strong electrostatic field near an ion reorganizes dipolar monomers, resulting in nonmonotonic changes in the volume fraction profile and the dielectric function of the polymers with respect to those of simple liquid mixtures. For the parameter sets used, the spatial variations near an ion can be in the range of 1 nm or larger, producing significant differences in the solvation energy among simple liquid mixtures, polymer blends, and block copolymers. The solvation energy of an ion depends substantially on the chain length in block copolymers; thus, our theory predicts the preferential solvation of ions arising from differences in chain length.

Hydration number of alkali metal ions determined by insertion in a conducting polymer

DEFF Research Database (Denmark)

Skaarup, Steen

2008-01-01

of all other water molecules whose properties are still influenced significantly by the cation. Knowing the hydration number is important when considering, for instance, the transport of Na+ and K+ in biological cell membranes, since their different behavior may depend on the details of ion hydration....... The solvation of alkali metal ions has been discussed for many years without a clear consensus. This work presents a systematic study of the hydration numbers of the 5 alkali metal ions, using the electrochemical insertion of the ions in a conducting polymer (polypyrrole containing the large immobile anion DBS...... direct calculation of the number of M+ ions entering the film, and therefore the inserted M+ mass. The mass of the water molecules is calculated as a difference. The results yield the following primary hydration numbers: Li+: 5.5-5.6; Na+: 4.0-4.1; K+: 2.0-2.5; Rb+: 0.6-1.2; Cs+: ~0. The most important...

Solvation structures of lithium halides in methanol–water mixtures

International Nuclear Information System (INIS)

Sarkar, Atanu; Dixit, Mayank Kumar; Tembe, B.L.

2015-01-01

Highlights: • Potentials of mean force for Li + -halides are calculated in methanol–water mixtures. • Stable CIP for x methanol = 1.0 becomes unstable at and below x methanol = 0.75. • The Li + ion is preferentially solvated by methanol molecules. • The halide ions are preferentially solvated by water molecules. - Abstract: The potentials of mean force (PMFs) for the ion pairs, Li + −Cl − , Li + −Br − and Li + −I − have been calculated in five methanol–water compositions. The results obtained are verified by trailing the trajectories and calculating the ion pair distance residence times. Local structures around the ions are studied using the radial distribution functions, density profiles, orientational correlation functions, running coordination numbers and excess coordination numbers. The major change in PMF is observed as the methanol mole fraction (x methanol ) is changed from 1.0 to 0.75. The stable contact ion pair occurring for x methanol = 1.0 becomes unstable at and below x methanol = 0.75. The preferential solvation data show that the halide ions are always preferentially solvated by water molecules. Although the lithium ion is preferentially solvated by methanol molecules, there is significant affinity towards water molecules as well

Preferential Solvation of an Asymmetric Redox Molecule

Energy Technology Data Exchange (ETDEWEB)

Han, Kee Sung; Rajput, Nav Nidhi; Vijayakumar, M.; Wei, Xiaoliang; Wang, Wei; Hu, Jian Z.; Persson, Kristin A.; Mueller, Karl T.

2016-12-15

The fundamental correlations between inter-molecular interactions, solvation structure and functionality of electrolytes are in many cases unknown, particularly for multi-component liquid systems. In this work, we explore such correlations by investigating the complex interplay between solubility and solvation structure for the electrolyte system comprising N-(ferrocenylmethyl)-N,N-dimethyl-N-ethylammonium bistrifluoromethylsulfonimide (Fc1N112-TFSI) dissolved in a ternary carbonate solvent mixture using combined NMR relaxation and computational analyses. Probing the evolution of the solvent-solvent, ion-solvent and ion-ion interactions with an increase in solute concentration provides a molecular level understanding of the solubility limit of the Fc1N112-TFSI system. An increase in solute con-centration leads to pronounced Fc1N112-TFSI contact-ion pair formation by diminishing solvent-solvent and ion-solvent type interactions. At the solubility limit, the precipitation of solute is initiated through agglomeration of contact-ion pairs due to overlapping solvation shells.

Revealing the Solvation Structure and Dynamics of Carbonate Electrolytes in Lithium-Ion Batteries by Two-Dimensional Infrared Spectrum Modeling.

Science.gov (United States)

Liang, Chungwen; Kwak, Kyungwon; Cho, Minhaeng

2017-12-07

Carbonate electrolytes in lithium-ion batteries play a crucial role in conducting lithium ions between two electrodes. Mixed solvent electrolytes consisting of linear and cyclic carbonates are commonly used in commercial lithium-ion batteries. To understand how the linear and cyclic carbonates introduce different solvation structures and dynamics, we performed molecular dynamics simulations of two representative electrolyte systems containing either linear or cyclic carbonate solvents. We then modeled their two-dimensional infrared (2DIR) spectra of the carbonyl stretching mode of these carbonate molecules. We found that the chemical exchange process involving formation and dissociation of lithium-ion/carbonate complexes is responsible for the growth of 2DIR cross peaks with increasing waiting time. In addition, we also found that cyclic carbonates introduce faster dynamics of dissociation and formation of lithium-ion/carbonate complexes than linear carbonates. These findings provide new insights into understanding the lithium-ion mobility and its interplay with solvation structure and ultrafast dynamics in carbonate electrolytes used in lithium-ion batteries.

Infrared Spectroscopy of Metal Ion Complexes: Models for Metal Ligand Interactions and Solvation

Science.gov (United States)

Duncan, Michael

2006-03-01

Weakly bound complexes of the form M^+-Lx (M=Fe, Ni, Co, etc.; L=CO2, C2H2, H2O, benzene, N2) are prepared in supersonic molecular beams by laser vaporization in a pulsed-nozzle cluster source. These species are mass analyzed and size-selected in a reflectron time-of-flight mass spectrometer. Clusters are photodissociated at infrared wavelengths with a Nd:YAG pumped infrared optical parametric oscillator/amplifier (OPO/OPA) laser or with a tunable infrared free-electron laser. M^+-(CO2)x complexes absorb near the free CO2 asymmetric stretch near 2349 cm-1 but with an interesting size dependent variation in the resonances. Small clusters have blue-shifted resonances, while larger complexes have additional bands due to surface CO2 molecules not attached to the metal. M^+(C2H2)n complexes absorb near the C-H stretches in acetylene, but resonances in metal complexes are red-shifted with repect to the isolated molecule. Ni^+ and Co^+ complexes with acetylene undergo intracluster cyclization reactions to form cyclobutadiene. Transition metal water complexes are studied in the O-H stretch region, and partial rotational structure can be measured. M^+(benzene) and M^+(benzene)2 ions (M=V, Ti, Al) represent half-sandwich and sandwich species, whose spectra are measured near the free benzene modes. These new IR spectra and their assignments will be discussed as well as other new IR spectra for similar complexes.

A conductivity study of preferential solvation of lithium ion in acetonitrile-dimethyl sulfoxide mixtures

International Nuclear Information System (INIS)

Mozhzhukhina, Nataliia; Longinotti, M. Paula; Corti, Horacio R.; Calvo, Ernesto J.

2015-01-01

The electrical mobility of LiPF 6 in acetonitrile–dimethyl sulfoxide (ACN–DMSO) mixtures, a potential electrolyte in oxygen cathodes of lithium-air batteries, has been studied using a very precise conductance technique, which allowed the determination of the infinite dilution molar conductivity and association constant of the salt in the whole composition range. In the search for preferential Li + ion solvation, we also measured the electrical conductivity of tetrabutylammonium hexafluorophosphate (TBAPF 6 ), a salt formed by a bulky cation, over the same composition range. The results show a qualitative change in the curvature of the LiPF 6 molar conductivity composition dependence for ACN molar fraction (x ACN ) ∼ 0.95, which was not observed for TBAPF 6 . The dependence of the measured Li/Li + couple potential with solvent composition also showed a pronounced change around the same composition. We suggest that these observations can be explained by Li + ion preferential solvation by DMSO in ACN–DMSO mixtures with very low molar fractions of DMSO

Biomolecular electrostatics and solvation: a computational perspective.

Science.gov (United States)

Ren, Pengyu; Chun, Jaehun; Thomas, Dennis G; Schnieders, Michael J; Marucho, Marcelo; Zhang, Jiajing; Baker, Nathan A

2012-11-01

An understanding of molecular interactions is essential for insight into biological systems at the molecular scale. Among the various components of molecular interactions, electrostatics are of special importance because of their long-range nature and their influence on polar or charged molecules, including water, aqueous ions, proteins, nucleic acids, carbohydrates, and membrane lipids. In particular, robust models of electrostatic interactions are essential for understanding the solvation properties of biomolecules and the effects of solvation upon biomolecular folding, binding, enzyme catalysis, and dynamics. Electrostatics, therefore, are of central importance to understanding biomolecular structure and modeling interactions within and among biological molecules. This review discusses the solvation of biomolecules with a computational biophysics view toward describing the phenomenon. While our main focus lies on the computational aspect of the models, we provide an overview of the basic elements of biomolecular solvation (e.g. solvent structure, polarization, ion binding, and non-polar behavior) in order to provide a background to understand the different types of solvation models.

Solid state cathode materials for secondary magnesium-ion batteries that are compatible with magnesium metal anodes in water-free electrolyte

International Nuclear Information System (INIS)

Crowe, Adam J.; Bartlett, Bart M.

2016-01-01

With high elemental abundance, large volumetric capacity, and dendrite-free metal deposition, magnesium metal anodes offer promise in beyond-lithium-ion batteries. However, the increased charge density associated with the divalent magnesium-ion (Mg 2+ ), relative to lithium-ion (Li + ) hinders the ion-insertion and extraction processes within many materials and structures known for lithium-ion cathodes. As a result, many recent investigations incorporate known amounts of water within the electrolyte to provide temporary solvation of the Mg 2+ , improving diffusion kinetics. Unfortunately with the addition of water, compatibility with magnesium metal anodes disappears due to forming an ion-insulating passivating layer. In this short review, recent advances in solid state cathode materials for rechargeable magnesium-ion batteries are highlighted, with a focus on cathode materials that do not require water contaminated electrolyte solutions for ion insertion and extraction processes. - Graphical abstract: In this short review, we present candidate materials for reversible Mg-battery cathodes that are compatible with magnesium metal in water-free electrolytes. The data suggest that soft, polarizable anions are required for reversible cycling.

Molecular Studies of Complex Soil Organic Matter Interactions with Metal Ions and Mineral Surfaces using Classical Molecular Dynamics and Quantum Chemistry Methods

Science.gov (United States)

Andersen, A.; Govind, N.; Laskin, A.

2017-12-01

Mineral surfaces have been implicated as potential protectors of soil organic matter (SOM) against decomposition and ultimate mineralization to small molecules which can provide nutrients for plants and soil microbes and can also contribute to the Earth's elemental cycles. SOM is a complex mixture of organic molecules of biological origin at varying degrees of decomposition and can, itself, self-assemble in such a way as to expose some biomolecule types to biotic and abiotic attack while protecting other biomolecule types. The organization of SOM and SOM with mineral surfaces and solvated metal ions is driven by an interplay of van der Waals and electrostatic interactions leading to partitioning of hydrophilic (e.g. sugars) and hydrophobic (e.g., lipids) SOM components that can be bridged with amphiphilic molecules (e.g., proteins). Classical molecular dynamics simulations can shed light on assemblies of organic molecules alone or complexation with mineral surfaces. The role of chemical reactions is also an important consideration in potential chemical changes of the organic species such as oxidation/reduction, degradation, chemisorption to mineral surfaces, and complexation with solvated metal ions to form organometallic systems. For the study of chemical reactivity, quantum chemistry methods can be employed and combined with structural insight provided by classical MD simulations. Moreover, quantum chemistry can also simulate spectroscopic signatures based on chemical structure and is a valuable tool in interpreting spectra from, notably, x-ray absorption spectroscopy (XAS). In this presentation, we will discuss our classical MD and quantum chemistry findings on a model SOM system interacting with mineral surfaces and solvated metal ions.

Ion exchange of some transition metal cations on hydrated titanium dioxide in aqueous ammonia solutions

International Nuclear Information System (INIS)

Bilewicz, A.; Narbutt, J.; Dybczynski, R.

1992-01-01

The adsorption of transition metal cations on hydrated titanium dioxide in complexing ammonia and amine solutions has been studied as a function of ammonia (amine) concentration. The relationships between the distribution coefficients and ammonia concentration as well as the effects of various amines on sorption of transition metals indicate that a coordinate bond is formed between the metal ions and the hydroxy groups of the sorbent. The distribution coefficients of silver(I) and cobalt(II), which form strong ammonia complexes in aqueous solutions, decrease with increasing concentration of ammonia already at concentrations exceeding 10 -3 *mol*dm -3 . Cations of zinc, manganese and mercury which form much weaker ammonia complexes do not exhibit any effect of ammonia concentration in the whole range investigated. In the case of sorption of macroamounts of ammonia or amine complexes of silver, the molecular sieve effect plays an important role. The differences in the affinity of hydrated titanium dioxide for ammonia solvates of various transition metal ions can serve as a tool for effective separation of these ions in ammonia solutions. (author) 10 refs.; 4 figs.; 1 tab

Advanced dielectric continuum model of preferential solvation

Science.gov (United States)

Basilevsky, Mikhail; Odinokov, Alexey; Nikitina, Ekaterina; Grigoriev, Fedor; Petrov, Nikolai; Alfimov, Mikhail

2009-01-01

A continuum model for solvation effects in binary solvent mixtures is formulated in terms of the density functional theory. The presence of two variables, namely, the dimensionless solvent composition y and the dimensionless total solvent density z, is an essential feature of binary systems. Their coupling, hidden in the structure of the local dielectric permittivity function, is postulated at the phenomenological level. Local equilibrium conditions are derived by a variation in the free energy functional expressed in terms of the composition and density variables. They appear as a pair of coupled equations defining y and z as spatial distributions. We consider the simplest spherically symmetric case of the Born-type ion immersed in the benzene/dimethylsulfoxide (DMSO) solvent mixture. The profiles of y(R ) and z(R ) along the radius R, which measures the distance from the ion center, are found in molecular dynamics (MD) simulations. It is shown that for a given solute ion z(R ) does not depend significantly on the composition variable y. A simplified solution is then obtained by inserting z(R ), found in the MD simulation for the pure DMSO, in the single equation which defines y(R ). In this way composition dependences of the main solvation effects are investigated. The local density augmentation appears as a peak of z(R ) at the ion boundary. It is responsible for the fine solvation effects missing when the ordinary solvation theories, in which z =1, are applied. These phenomena, studied for negative ions, reproduce consistently the simulation results. For positive ions the simulation shows that z ≫1 (z =5-6 at the maximum of the z peak), which means that an extremely dense solvation shell is formed. In such a situation the continuum description fails to be valid within a consistent parametrization.

Compound forming extractants, solvating solvents and inert solvents IUPAC chemical data series

CERN Document Server

Marcus, Y; Kertes, A S

2013-01-01

Equilibrium Constants of Liquid-Liquid Distribution Reactions, Part III: Compound Forming Extractants, Solvating Solvents, and Inert Solvents focuses on the compilation of equilibrium constants of various compounds, such as acids, ions, salts, and aqueous solutions. The manuscript presents tables that show the distribution reactions of carboxylic and sulfonic acid extractants and their dimerization and other reactions in the organic phase and extraction reactions of metal ions from aqueous solutions. The book also states that the inorganic anions in these solutions are irrelevant, since they d

Affine-response model of molecular solvation of ions: Accurate predictions of asymmetric charging free energies

Czech Academy of Sciences Publication Activity Database

Bardhan, J. P.; Jungwirth, Pavel; Makowski, L.

Roč. 137, č. 12 ( 2012 ), 124101/1-124101/6 ISSN 0021-9606 R&D Projects: GA MŠk LH12001 Institutional research plan: CEZ:AV0Z40550506 Keywords : ion solvation * continuum models * linear response Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.164, year: 2012

DFT study of the interaction between DOTA chelator and competitive alkali metal ions.

Science.gov (United States)

Frimpong, E; Skelton, A A; Honarparvar, B

2017-09-01

1, 4, 7, 10-tetraazacyclododecane-1, 4, 7, 10-tetracetic acid (DOTA) is an important chelator for radiolabeling of pharmaceuticals. The ability of alkali metals found in the body to complex with DOTA and compete with radio metal ions can alter the radiolabeling process. Non-covalent interactions between DOTA complexed with alkali metals Li + , Na + , K + and Rb + , are investigated with density functional theory using B3LYP and ωB97XD functionals. Conformational possibilities of DOTA were explored with a varying number of carboxylic pendant arms of DOTA in close proximity to the ions. It is found that the case in which four arms of DOTA are interacting with ions is more stable than other conformations. The objective of this study is to explore the electronic structure properties upon complexation of alkali metals Li + Na + , K + and Rb + with a DOTA chelator. Interaction energies, relaxation energies, entropies, Gibbs free energies and enthalpies show that the stability of DOTA, complexed with alkali metals decreases down the group of the periodic table. Implicit water solvation affects the complexation of DOTA-ions leading to decreases in the stability of the complexes. NBO analysis through the natural population charges and the second order perturbation theory, revealed a charge transfer between DOTA and alkali metals. Conceptual DFT-based properties such as HOMO/LUMO energies, ΔE HOMO-LUMO and chemical hardness and softness indicated a decrease in the chemical stability of DOTA-alkali metal complexes down the alkali metal series. This study serves as a guide to researchers in the field of organometallic chelators, particularly, radiopharmaceuticals in finding the efficient optimal match between chelators and various metal ions. Copyright © 2017 Elsevier Inc. All rights reserved.

Analysis of metals in solution using electrospray ionization mass spectrometry

International Nuclear Information System (INIS)

Van Berkel, G.J.; McLuckey, S.A.; Glish, G.L.

1991-01-01

Electrospray ionization-mass spectrometry (ES-MS) has gained most of its recent attention because of the ability to produce multiply charged ions from very large biomolecules making them amenable to analysis by most modern mass spectrometers. However, ES-MS is equally well suited for compounds of low or moderate molecular weight that are difficult to volatilize intact by others methods. Moreover, the early work of Fenn and co-workers (1,2) and recent reports by Kebarle and co-workers (3,4) attest to the applicability of ES-MS to the study of the gas-phase chemistry of multiply solvated or coordinated metal ions. The utility of ES-MS for the analysis of metals in solution derives in part from the facility with which the metal ions are solvated by or form complexes with the ES solvent or other reagents added to the solvent. Solvation and complexation can be a hindrance, however, in the analytical application of ES-MS to the analysis of metals in solution, especially solutions of metals in water. The data presented here demonstrate that many of the problems in the ES-MS analysis of metals can be overcome by complexing the metals with crown ethers and/or extracting the metals from water into an organic phase using crown ethers. 5 refs., 4 figs

Towards a stable ion-solvating polymer electrolyte for advanced alkaline water electrolysis

DEFF Research Database (Denmark)

Aili, David; Wright, Andrew G.; Kraglund, Mikkel Rykær

2017-01-01

Advanced alkaline water electrolysis using ion-solvating polymer membranes as electrolytes represents a new direction in the field of electrochemical hydrogen production. Polybenzimidazole membranes equilibrated in aqueous KOH combine the mechanical robustness and gas-tightness of a polymer...... stability in alkaline environments. The novel electrolytes are extensively characterized with respect to physicochemical and electrochemical properties and the chemical stability is assessed in 0-50 wt% aqueous KOH for more than 6 months at 88 degrees C. In water electrolysis tests using porous 3...

Microscopic solvation of a lithium atom in water-ammonia mixed clusters: solvent coordination and electron localization in presence of a counterion.

Science.gov (United States)

Pratihar, Subha; Chandra, Amalendu

2008-07-14

The microsolvation structures and energetics of water-ammonia mixed clusters containing a lithium atom, i.e., Li(H(2)O)(n)(NH(3)), n = 1-5, are investigated by means of ab initio theoretical calculations. Several structural aspects such as the solvent coordination to the metal ion and binding motifs of the free valence electron of the metal are investigated. We also study the energetics aspects such as the dependence of vertical ionization energies on the cluster size, and all these structural and energetics aspects are compared to the corresponding results of previously studied anionic water-ammonia clusters without a metal ion. It is found that the Li-O and Li-N interactions play a very important role in stabilizing the lithium-water-ammonia clusters, and the presence of these metal ion-solvent interactions also affect the characteristics of electron solvation in these clusters. This is seen from the spatial distribution of the singly occupied molecular orbital (SOMO) which holds the ejected valence electron of the Li atom. For very small clusters, SOMO electron density is found to exist mainly at the vicinity of the Li atom, whereas for larger clusters, it is distributed outside the first solvation shell. The free dangling hydrogens of water and ammonia molecules are involved in capturing the SOMO electron density. In some of the conformers, OH{e}HO and OH{e}HN types of interactions are found to be present. The presence of the metal ion at the center of the cluster ensures that the ejected electron is solvated at a surface state only, whereas both surface and interiorlike states were found for the free electron in the corresponding anionic clusters without a metal ion. The vertical ionization energies of the present clusters are found to be higher than the vertical detachment energies of the corresponding anionic clusters which signify a relatively stronger binding of the free electron in the presence of the positive metal counterion. The shifts in different

Solvation thermodynamics and heat capacity of polar and charged solutes in water

Science.gov (United States)

Sedlmeier, Felix; Netz, Roland R.

2013-03-01

The solvation thermodynamics and in particular the solvation heat capacity of polar and charged solutes in water is studied using atomistic molecular dynamics simulations. As ionic solutes we consider a F- and a Na+ ion, as an example for a polar molecule with vanishing net charge we take a SPC/E water molecule. The partial charges of all three solutes are varied in a wide range by a scaling factor. Using a recently introduced method for the accurate determination of the solvation free energy of polar solutes, we determine the free energy, entropy, enthalpy, and heat capacity of the three different solutes as a function of temperature and partial solute charge. We find that the sum of the solvation heat capacities of the Na+ and F- ions is negative, in agreement with experimental observations, but our results uncover a pronounced difference in the heat capacity between positively and negatively charged groups. While the solvation heat capacity ΔCp stays positive and even increases slightly upon charging the Na+ ion, it decreases upon charging the F- ion and becomes negative beyond an ion charge of q = -0.3e. On the other hand, the heat capacity of the overall charge-neutral polar solute derived from a SPC/E water molecule is positive for all charge scaling factors considered by us. This means that the heat capacity of a wide class of polar solutes with vanishing net charge is positive. The common ascription of negative heat capacities to polar chemical groups might arise from the neglect of non-additive interaction effects between polar and apolar groups. The reason behind this non-additivity is suggested to be related to the second solvation shell that significantly affects the solvation thermodynamics and due to its large spatial extent induces quite long-ranged interactions between solvated molecular parts and groups.

Studies of base pair sequence effects on DNA solvation based on all

Indian Academy of Sciences (India)

Detailed analyses of the sequence-dependent solvation and ion atmosphere of DNA are presented based on molecular dynamics (MD) simulations on all the 136 unique tetranucleotide steps obtained by the ABC consortium using the AMBER suite of programs. Significant sequence effects on solvation and ion localization ...

Luminescence study on solvation of americium(III), curium(III) and several lanthanide(III) ions in nonaqueous and binary mixed solvents

International Nuclear Information System (INIS)

Kimura, T.; Nagaishi, R.; Kato, Y.; Yoshida, Z.

2001-01-01

The luminescence lifetimes of An(III) and Ln(III) ions [An=Am and Cm; Ln=Nd, Sm, Eu, Tb and Dy] were measured in dimethyl sulfoxide(DMSO), N,N-dimethylformamide(DMF), methanol(MeOH), water and their perdeuterated solvents. Nonradiative decay rates of the ions were in the order of H 2 O > MeOH > DMF > DMSO, indicating that O-H vibration is more effective quencher than C-H, C=O, and S=O vibrations in the solvent molecules. Maximal lifetime ratios τ D /τ H were observed for Eu(III) in H 2 O, for Sm(III) in MeOH and DMF, and for Sm(III) and Dy(III) in DMSO. The solvent composition in the first coordination sphere of Cm(III) and Ln(III) in binary mixed solvents was also studied by measuring the luminescence lifetime. Cm(III) and Ln(III) were preferentially solvated by DMSO in DMSO-H 2 O, by DMF in DMF-H 2 O, and by H 2 O in MeOH-H 2 O over the whole range of the solvent composition. The order of the preferential solvation, i.e., DMSO > DMF > H 2 O > MeOH, correlates with the relative basicity of these solvents. The Gibbs free energy of transfer of ions from water to nonaqueous solvents was further estimated from the degree of the preferential solvation. (orig.)

Freezing hot electrons. Electron transfer and solvation dynamics at D{sub 2}O and NH{sub 3}-metal interfaces

Energy Technology Data Exchange (ETDEWEB)

Staehler, A.J.

2007-05-15

The present work investigates the electron transfer and solvation dynamics at the D{sub 2}O/Cu(111), D{sub 2}O/Ru(001), and NH{sub 3}/Cu(111) interfaces using femtosecond time-resolved two-photon photoelectron spectroscopy. Within this framework, the influence of the substrate, adsorbate structure and morphology, solvation site, coverage, temperature, and solvent on the electron dynamics are studied, yielding microscopic insight into the underlying fundamental processes. Transitions between different regimes of ET, substrate-dominated, barrier-determined, strong, and weak coupling are observed by systematic variation of the interfacial properties and development of empirical model descriptions. It is shown that the fundamental steps of the interfacial electron dynamics are similar for all investigated systems: Metal electrons are photoexcited to unoccupied metal states and transferred into the adlayer via the adsorbate's conduction band. The electrons localize at favorable sites and are stabilized by reorientations of the surrounding polar solvent molecules. Concurrently, they decay back two the metal substrate, as it offers a continuum of unoccupied states. However, the detailed characteristics vary for the different investigated interfaces: For amorphous ice-metal interfaces, the electron transfer is initially, right after photoinjection, dominated by the substrate's electronic surface band structure. With increasing solvation, a transient barrier evolves at the interface that increasingly screens the electrons from the substrate. Tunneling through this barrier becomes the rate-limiting step for ET. The competition of electron decay and solvation leads to lifetimes of the solvated electrons in the order of 100 fs. Furthermore, it is shown that the electrons bind in the bulk of the ice layers, but on the edges of adsorbed D{sub 2}O clusters and that the ice morphology strongly influences the electron dynamics. For the amorphous NH{sub 3}/Cu(111

Proton solvation and proton transfer in chemical and electrochemical processes

International Nuclear Information System (INIS)

Lengyel, S.; Conway, B.E.

1983-01-01

This chapter examines the proton solvation and characterization of the H 3 O + ion, proton transfer in chemical ionization processes in solution, continuous proton transfer in conductance processes, and proton transfer in electrode processes. Topics considered include the condition of the proton in solution, the molecular structure of the H 3 O + ion, thermodynamics of proton solvation, overall hydration energy of the proton, hydration of H 3 O + , deuteron solvation, partial molal entropy and volume and the entropy of proton hydration, proton solvation in alcoholic solutions, analogies to electrons in semiconductors, continuous proton transfer in conductance, definition and phenomenology of the unusual mobility of the proton in solution, solvent structure changes in relation to anomalous proton mobility, the kinetics of the proton-transfer event, theories of abnormal proton conductance, and the general theory of the contribution of transfer reactions to overall transport processes

Nonpolar solvation dynamics for a nonpolar solute in room ...

Indian Academy of Sciences (India)

Sandipa Indra

2018-01-30

Jan 30, 2018 ... Keywords. Solvation dynamics; nonpolar solvation; ionic liquid; molecular dynamics; linear response theory. 1. ... J. Chem. Sci. (2018) 130:3 spectrum of the excited probe molecule for imida- .... Therefore, the solute and the RTIL ions interact only ... interval of 30 ps from a long equilibrium trajectory of dura-.

Preferential Solvation of Silver (I) Bromate in Methanol-Dimethylsulfoxide Mixtures

Science.gov (United States)

Janardhanan, S.; Kalidas, C.

1984-06-01

The solubiltiy of silver bromate, the Gibbs transfer energy of Ag+ and BrO3- and the solvent transport number in methanol-dimethyl sulfoxide mixtures are reported. The solubility of silver bromate increases with addition of DMSO. The Gibbs energy of transfer of the silver ion (based on the ferrocene reference method) decreases, while that of the bromate ion becomes slightly negative with the addition of DMSO. The solvent transport number A passes through a maximum (⊿ = 1.0 at XDMSO = 0.65. From these results, it is concluded that the silver ion is preferentially solvated by DMSO whereas the bromate ion shows no preferential solvation.

A dual cryogenic ion trap spectrometer for the formation and characterization of solvated ionic clusters

Energy Technology Data Exchange (ETDEWEB)

Marsh, Brett M.; Voss, Jonathan M.; Garand, Etienne, E-mail: egarand@chem.wisc.edu [Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706 (United States)

2015-11-28

A new experimental approach is presented in which two separate cryogenic ion traps are used to reproducibly form weakly bound solvent clusters around electrosprayed ions and messenger-tag them for single-photon infrared photodissociation spectroscopy. This approach thus enables the vibrational characterization of ionic clusters comprised of a solvent network around large and non-volatile ions. We demonstrate the capabilities of the instrument by clustering water, methanol, and acetone around a protonated glycylglycine peptide. For water, cluster sizes with greater than twenty solvent molecules around a single ion are readily formed. We further demonstrate that similar water clusters can be formed around ions having a shielded charge center or those that do not readily form hydrogen bonds. Finally, infrared photodissociation spectra of D{sub 2}-tagged GlyGlyH{sup +} ⋅ (H{sub 2}O){sub 1−4} are presented. They display well-resolved spectral features and comparisons with calculations reveal detailed information on the solvation structures of this prototypical peptide.

Understanding Lithium Solvation and Diffusion through Topological Analysis of First-Principles Molecular Dynamics

Energy Technology Data Exchange (ETDEWEB)

Bhatia, Harsh [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Gyulassy, Attila [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Ong, Mitchell [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Lordi, Vincenzo [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Draeger, Erik [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Pask, John [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Pascucci, Valerio [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Bremer, Peer -Timo [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

2016-09-27

The performance of lithium-ion batteries is strongly influenced by the ionic conductivity of the electrolyte, which depends on the speed at which Li ions migrate across the cell and relates to their solvation structure. The choice of solvent can greatly impact, both, the solvation and diffusivity of Li ions. In this work, we present our application of the topological techniques to extract and predict such behavior in the data generated by the first-principles molecular dynamics simulation of Li ions in an important organic solvent -ethylene carbonate. More specifically, we use the scalar topology of the electron charge density field to analyze the evolution of the solvation structures. This allows us to derive a parameter-free bond definition for lithium-oxygen bonds, to provide a quantitative measure for bond strength, and to understand the regions of influence of each atom in the simulation. This has provided new insights into how and under what conditions certain bonds may form and break. As a result, we can identify and, more importantly, predict, unstable configurations in solvation structures. This can be very useful in understanding when small changes to the atoms' movements can cause significantly different bond structures to evolve. Ultimately, this promises to allow scientists to explore lithium ion solvation and diffusion more systematically, with the aim of new insights and potentially accelerating the calculations themselves.

Formation of clusters (ions solvated with products of radiolysis) during irradiation of certain chloralkanes in the condensed phase

International Nuclear Information System (INIS)

Sukhov, F.F.; Karatun, A.A.; Slovokhotova, N.A.

1983-01-01

Using the infrared spectroscopy method, the radiolysis of the 2-chloropropane and 2-chloro-2-methylpropane was investigated in various phase states and in argon matrix at 15 and 77 K. A conclusion is drawn that the reaction of the radiation dehydrochlorination in the chloralkanes investigated occurs under certain conditions in the vicinity of ions, mostly; as this takes place, unique clusters composed of radiolysis products, i.e. ions solvated with complexes of alkane and hydrogen chloride are being formed. (author)

Internal energy effects on the solvation and reactivity of multiply charged biomolecules for electrospray ionization mass spectroscopy. [Bovine ubiquitin

Energy Technology Data Exchange (ETDEWEB)

Light-Wahl, K.J.; Winger, B.E.; Rockwood, A.L.; Smith, R.D.

1992-06-01

Mild (capillary) interface conditions which do not completely desolvate the ions of proteins in electrospray ionization mass spectrometry (ESI-MS) may be required to probe the higher order structures and weak associations. For the small protein bovine ubiquitin, two ion distributions (unsolvated ions and unresolved solvated ions) were observed. The resolvable solvation for leucine-enkephalin with methanol and water shows that the use of countercurrent N{sub 2} flow at the capillary affects the solvation observed. 2 figs. (DLC)

Electrostatic solvation free energies of charged hard spheres using molecular dynamics with density functional theory interactions

Science.gov (United States)

Duignan, Timothy T.; Baer, Marcel D.; Schenter, Gregory K.; Mundy, Chistopher J.

2017-10-01

Determining the solvation free energies of single ions in water is one of the most fundamental problems in physical chemistry and yet many unresolved questions remain. In particular, the ability to decompose the solvation free energy into simple and intuitive contributions will have important implications for models of electrolyte solution. Here, we provide definitions of the various types of single ion solvation free energies based on different simulation protocols. We calculate solvation free energies of charged hard spheres using density functional theory interaction potentials with molecular dynamics simulation and isolate the effects of charge and cavitation, comparing to the Born (linear response) model. We show that using uncorrected Ewald summation leads to unphysical values for the single ion solvation free energy and that charging free energies for cations are approximately linear as a function of charge but that there is a small non-linearity for small anions. The charge hydration asymmetry for hard spheres, determined with quantum mechanics, is much larger than for the analogous real ions. This suggests that real ions, particularly anions, are significantly more complex than simple charged hard spheres, a commonly employed representation.

Metal ion transporters and homeostasis.

OpenAIRE

Nelson, N

1999-01-01

Transition metals are essential for many metabolic processes and their homeostasis is crucial for life. Aberrations in the cellular metal ion concentrations may lead to cell death and severe diseases. Metal ion transporters play a major role in maintaining the correct concentrations of the various metal ions in the different cellular compartments. Recent studies of yeast mutants revealed key elements in metal ion homeostasis, including novel transport systems. Several of the proteins discover...

Competitive solvation of (bis)(trifluoromethanesulfonyl)imide anion by acetonitrile and water

DEFF Research Database (Denmark)

Chaban, Vitaly

2014-01-01

Competitive solvation of an ion by two or more solvents is one of the key phenomena determining the identity of our world. Solvation in polar solvents frequently originates from non-additive non-covalent interactions. Pre-parametrized potentials poorly capture these interactions, unless the force...

Solvation of positive ions in water: the dominant role of water-water interaction

International Nuclear Information System (INIS)

Krekeler, Christian; Site, Luigi Delle

2007-01-01

Local polarization effects, induced by monovalent and divalent positive ions in water, influence (and in turn are influenced by) the large-scale structural properties of the solvent. Experiments can only distinguish this process of interplay in a generic qualitative way. Instead, first-principles calculations can address the question at both the electronic and atomistic scale, accounting for electronic polarization as well as geometrical conformations. For this reason we study the extension of the scales' interconnection by means of first-principle Car-Parrinello molecular dynamics applied to systems of different size. In this way we identify the general aspects dominating the physics of the first solvation shell and their connection to the effects related to the formation of the outer shells and eventually the bulk. We show that while the influence of the ions is extended to the first shell only, the water-water interaction is instead playing a dominant role even within the first shell independently of the size or the charge of the ion. (fast track communication)

Theories of the solvated electron

International Nuclear Information System (INIS)

Kestner, N.R.

1987-01-01

In this chapter the authors address only the final state of the electron, that is, the solvated state, which, if no chemical reaction would occur, is a stable entity with well-defined characteristics. Except for some metal-ammonia solutions, and possible a few other cases, such stable species, in reality, exist but a short time (often as short as microseconds). Nevertheless, this chapter only deals with this final time-independent,'' completely solvated,'' equilibrium species. The last statement is added to indicate that the solvent around the electron has also come to thermal equilibrium with the field of the charge

Standard electrode potential, Tafel equation, and the solvation thermodynamics.

Science.gov (United States)

Matyushov, Dmitry V

2009-06-21

Equilibrium in the electronic subsystem across the solution-metal interface is considered to connect the standard electrode potential to the statistics of localized electronic states in solution. We argue that a correct derivation of the Nernst equation for the electrode potential requires a careful separation of the relevant time scales. An equation for the standard metal potential is derived linking it to the thermodynamics of solvation. The Anderson-Newns model for electronic delocalization between the solution and the electrode is combined with a bilinear model of solute-solvent coupling introducing nonlinear solvation into the theory of heterogeneous electron transfer. We therefore are capable of addressing the question of how nonlinear solvation affects electrochemical observables. The transfer coefficient of electrode kinetics is shown to be equal to the derivative of the free energy, or generalized force, required to shift the unoccupied electronic level in the bulk. The transfer coefficient thus directly quantifies the extent of nonlinear solvation of the redox couple. The current model allows the transfer coefficient to deviate from the value of 0.5 of the linear solvation models at zero electrode overpotential. The electrode current curves become asymmetric in respect to the change in the sign of the electrode overpotential.

Phase Equilibria and Ionic Solvation in the Lithium Tetrafluoroborate-Dimethylsulfoxide System

Science.gov (United States)

Gafurov, M. M.; Kirillov, S. A.; Gorobets, M. I.; Rabadanov, K. Sh.; Ataev, M. B.; Tretyakov, D. O.; Aydemirov, K. M.

2015-01-01

The phase diagram and electrical conductivity isotherms for the lithium tetrafluoroborate (LiBF4)-dimethylsulfoxide (DMSO) system and Raman spectra of DMSO and the LiBF4-DMSO solution were studied. Spectroscopic signatures of a H-bond between DMSO and BF4 - ions were found. The bonds of Li+ ions to the solvent were stronger than the bonds in DMSO dimers because formation of the solvate destroyed dimeric DMSO molecules. The τω values for DMSO molecules in the Li+-ion solvate shell of the LiBF4-DMSO system were similar to those for associated solvent molecules.

Refined Dummy Atom Model of Mg(2+) by Simple Parameter Screening Strategy with Revised Experimental Solvation Free Energy.

Science.gov (United States)

Jiang, Yang; Zhang, Haiyang; Feng, Wei; Tan, Tianwei

2015-12-28

Metal ions play an important role in the catalysis of metalloenzymes. To investigate metalloenzymes via molecular modeling, a set of accurate force field parameters for metal ions is highly imperative. To extend its application range and improve the performance, the dummy atom model of metal ions was refined through a simple parameter screening strategy using the Mg(2+) ion as an example. Using the AMBER ff03 force field with the TIP3P model, the refined model accurately reproduced the experimental geometric and thermodynamic properties of Mg(2+). Compared with point charge models and previous dummy atom models, the refined dummy atom model yields an enhanced performance for producing reliable ATP/GTP-Mg(2+)-protein conformations in three metalloenzyme systems with single or double metal centers. Similar to other unbounded models, the refined model failed to reproduce the Mg-Mg distance and favored a monodentate binding of carboxylate groups, and these drawbacks needed to be considered with care. The outperformance of the refined model is mainly attributed to the use of a revised (more accurate) experimental solvation free energy and a suitable free energy correction protocol. This work provides a parameter screening strategy that can be readily applied to refine the dummy atom models for metal ions.

Evaluation of complexing agents and column temperature in ion chromatographic separation of alkali metals, alkaline earth metals and transition metals ion

International Nuclear Information System (INIS)

Kelkar, Anoop; Pandey, Ashish; Name, Anil B.; Das, D.K.; Behere, P.G.; Mohd Afzal

2015-01-01

The aim of ion chromatography method development is the resolution of all metal ions of interests. Resolution can be improved by changing the selectivity. Selectivity in chromatography can be altered by changes in mobile phase (eg eluent type, eluent strength) or through changes in stationary phase. Temperature has been used in altering the selectivity of particularly in reversed phase liquid chromatography and ion exchange chromatography. Present paper describe the retention behaviour of alkali metals, alkaline earth metals and transition metal ions on a silica based carboxylate function group containing analyte column. Alkali metals, alkaline earth metals and transition metal ions were detected by ion conductivity and UV-VIS detectors respectively

Theoretical Investigation of the Effect of the Rare Gas Matrices on the Vibrational Spectra of Solvated Molecular Ions: Cu+CO

Czech Academy of Sciences Publication Activity Database

Bludský, Ota; Šilhan, Martin; Nachtigall, Petr

2002-01-01

Roč. 117, č. 20 (2002), s. 9298-9305 ISSN 0021-9606 R&D Projects: GA MŠk LN00A032 Institutional research plan: CEZ:AV0Z4040901 Keywords : vibrational spectra * solvated molecular ions Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.998, year: 2002

Ion implantation and amorphous metals

International Nuclear Information System (INIS)

Hohmuth, K.; Rauschenbach, B.

1981-01-01

This review deals with ion implantation of metals in the high concentration range for preparing amorphous layers (>= 10 at%, implantation doses > 10 16 ions/cm 2 ). Different models are described concerning formation of amorphous phases of metals by ion implantation and experimental results are given. The study of amorphous phases has been carried out by the aid of Rutherford backscattering combined with the channeling technique and using transmission electron microscopy. The structure of amorphous metals prepared by ion implantation has been discussed. It was concluded that amorphous metal-metalloid compounds can be described by a dense-random-packing structure with a great portion of metal atoms. Ion implantation has been compared with other techniques for preparing amorphous metals and the adventages have been outlined

Ion implantation in metals

International Nuclear Information System (INIS)

Vook, F.L.

1977-02-01

The application of ion beams to metals is rapidly emerging as a promising area of research and technology. This report briefly describes some of the recent advances in the modification and study of the basic properties of metals by ion implantation techniques. Most of the research discussed illustrates some of the new and exciting applications of ion beams to metals which are under active investigation at Sandia Laboratories, Albuquerque

Incorporating Born solvation energy into the three-dimensional Poisson-Nernst-Planck model to study ion selectivity in KcsA K+ channels

Science.gov (United States)

Liu, Xuejiao; Lu, Benzhuo

2017-12-01

Potassium channels are much more permeable to potassium than sodium ions, although potassium ions are larger and both carry the same positive charge. This puzzle cannot be solved based on the traditional Poisson-Nernst-Planck (PNP) theory of electrodiffusion because the PNP model treats all ions as point charges, does not incorporate ion size information, and therefore cannot discriminate potassium from sodium ions. The PNP model can qualitatively capture some macroscopic properties of certain channel systems such as current-voltage characteristics, conductance rectification, and inverse membrane potential. However, the traditional PNP model is a continuum mean-field model and has no or underestimates the discrete ion effects, in particular the ion solvation or self-energy (which can be described by Born model). It is known that the dehydration effect (closely related to ion size) is crucial to selective permeation in potassium channels. Therefore, we incorporated Born solvation energy into the PNP model to account for ion hydration and dehydration effects when passing through inhomogeneous dielectric channel environments. A variational approach was adopted to derive a Born-energy-modified PNP (BPNP) model. The model was applied to study a cylindrical nanopore and a realistic KcsA channel, and three-dimensional finite element simulations were performed. The BPNP model can distinguish different ion species by ion radius and predict selectivity for K+ over Na+ in KcsA channels. Furthermore, ion current rectification in the KcsA channel was observed by both the PNP and BPNP models. The I -V curve of the BPNP model for the KcsA channel indicated an inward rectifier effect for K+ (rectification ratio of ˜3 /2 ) but indicated an outward rectifier effect for Na+ (rectification ratio of ˜1 /6 ) .

Interfacial solvation thermodynamics

International Nuclear Information System (INIS)

Ben-Amotz, Dor

2016-01-01

Previous studies have reached conflicting conclusions regarding the interplay of cavity formation, polarizability, desolvation, and surface capillary waves in driving the interfacial adsorptions of ions and molecules at air–water interfaces. Here we revisit these questions by combining exact potential distribution results with linear response theory and other physically motivated approximations. The results highlight both exact and approximate compensation relations pertaining to direct (solute–solvent) and indirect (solvent–solvent) contributions to adsorption thermodynamics, of relevance to solvation at air–water interfaces, as well as a broader class of processes linked to the mean force potential between ions, molecules, nanoparticles, proteins, and biological assemblies. (paper)

Zero-point energy effects in anion solvation shells.

Science.gov (United States)

Habershon, Scott

2014-05-21

By comparing classical and quantum-mechanical (path-integral-based) molecular simulations of solvated halide anions X(-) [X = F, Cl, Br and I], we identify an ion-specific quantum contribution to anion-water hydrogen-bond dynamics; this effect has not been identified in previous simulation studies. For anions such as fluoride, which strongly bind water molecules in the first solvation shell, quantum simulations exhibit hydrogen-bond dynamics nearly 40% faster than the corresponding classical results, whereas those anions which form a weakly bound solvation shell, such as iodide, exhibit a quantum effect of around 10%. This observation can be rationalized by considering the different zero-point energy (ZPE) of the water vibrational modes in the first solvation shell; for strongly binding anions, the ZPE of bound water molecules is larger, giving rise to faster dynamics in quantum simulations. These results are consistent with experimental investigations of anion-bound water vibrational and reorientational motion.

Metal Ion Controlled Polymorphism of a Peptide

DEFF Research Database (Denmark)

Hemmingsen, Lars Bo Stegeager; Jancso, Attila; Szunyogh, Daniel

2011-01-01

ions on fully or partially unstructured proteins, or the effect of metal ions on protein aggregation. Metal ions may be employed to fold (or misfold) individual peptides in a controlled manner depending on the potential metal ion coordinating amino acid side chains (Cys, His, Asp, Glu......In this work a metal ion binding model dodecapeptide was investigated in terms of its capacity to adopt different structures depending on the metal ion to peptide stoichiometry. The dodecapeptide is much simpler than real proteins, yet displays sufficient complexity to model the effect of metal......, …) in the peptide, and the ligand and structural preferences of the metal ion (in our studies Zn2+, Cd2+, Hg2+, Cu+/2+). Simultaneously, new species such as metal ion bridged ternary complexes or even oligomers may be formed. In recent previous studies we have observed similar polymorphism of zinc finger model...

Improving accuracy of electrochemical capacitance and solvation energetics in first-principles calculations

Science.gov (United States)

Sundararaman, Ravishankar; Letchworth-Weaver, Kendra; Schwarz, Kathleen A.

2018-04-01

Reliable first-principles calculations of electrochemical processes require accurate prediction of the interfacial capacitance, a challenge for current computationally efficient continuum solvation methodologies. We develop a model for the double layer of a metallic electrode that reproduces the features of the experimental capacitance of Ag(100) in a non-adsorbing, aqueous electrolyte, including a broad hump in the capacitance near the potential of zero charge and a dip in the capacitance under conditions of low ionic strength. Using this model, we identify the necessary characteristics of a solvation model suitable for first-principles electrochemistry of metal surfaces in non-adsorbing, aqueous electrolytes: dielectric and ionic nonlinearity, and a dielectric-only region at the interface. The dielectric nonlinearity, caused by the saturation of dipole rotational response in water, creates the capacitance hump, while ionic nonlinearity, caused by the compactness of the diffuse layer, generates the capacitance dip seen at low ionic strength. We show that none of the previously developed solvation models simultaneously meet all these criteria. We design the nonlinear electrochemical soft-sphere solvation model which both captures the capacitance features observed experimentally and serves as a general-purpose continuum solvation model.

Metal ion implantation: Conventional versus immersion

International Nuclear Information System (INIS)

Brown, I.G.; Anders, A.; Anders, S.; Dickinson, M.R.; MacGill, R.A.

1994-01-01

Vacuum-arc-produced metal plasma can be used as the ion feedstock material in an ion source for doing conventional metal ion implantation, or as the immersing plasma for doing plasma immersion ion implantation. The basic plasma production method is the same in both cases; it is simple and efficient and can be used with a wide range of metals. Vacuum arc ion sources of different kinds have been developed by the authors and others and their suitability as a metal ion implantation tool has been well established. Metal plasma immersion surface processing is an emerging tool whose characteristics and applications are the subject of present research. There are a number of differences between the two techniques, both in the procedures used and in the modified surfaces created. For example, the condensibility of metal plasma results in thin film formation and subsequent energetic implantation is thus done through the deposited layer; in the usual scenario, this recoil implantation and the intermixing it produces is a feature of metal plasma immersion but not of conventional energetic ion implantation. Metal plasma immersion is more suited (but not limited) to higher doses (>10 17 cm -2 ) and lower energies (E i < tens of keV) than the usual ranges of conventional metal ion implantation. These and other differences provide these vacuum-arc-based surface modification tools with a versatility that enhances the overall technological attractiveness of both

Evaluation of Stability of Complexes of Inner Transition Metal Ions with 2-Oxo-1-pyrrolidine Acetamide and Role of Systematic Errors

Directory of Open Access Journals (Sweden)

Sangita Sharma

2011-01-01

Full Text Available BEST FIT models were used to study the complexation of inner transition metal ions like Y(III, La(III, Ce(III, Pr(III, Nd(III, Sm(III, Gd(III, Dy(III and Th(IV with 2-oxo-1-pyrrolidine acetamide at 30 °C in 10%, 20, 30, 40, 50% and 60% v/v dioxane-water mixture at 0.2 M ionic strength. Irving Rossotti titration method was used to get titration data. Calculations were carried out with PKAS and BEST Fortran IV computer programs. The expected species like L, LH+, ML, ML2 and ML(OH3, were obtained with SPEPLOT. Stability of complexes has increased with increasing the dioxane content. The observed change in stability can be explained on the basis of electrostatic effects, non electrostatic effects, solvating power of solvent mixture, interaction between ions and interaction of ions with solvents. Effect of systematic errors like effect of dissolved carbon dioxide, concentration of alkali, concentration of acid, concentration of ligand and concentration of metal have also been explained here.

New developments in metal ion implantation by vacuum arc ion sources and metal plasma immersion

International Nuclear Information System (INIS)

Brown, I.G.; Anders, A.; Anders, S.

1996-01-01

Ion implantation by intense beams of metal ions can be accomplished using the dense metal plasma formed in a vacuum arc discharge embodied either in a vacuum arc ion source or in a metal plasma immersion configuration. In the former case high energy metal ion beams are formed and implantation is done in a more-or-less conventional way, and in the latter case the substrate is immersed in the plasma and repetitively pulse-biased so as to accelerate the ions at the high voltage plasma sheath formed at the substrate. A number of advances have been made in the last few years, both in plasma technology and in the surface modification procedures, that enhance the effectiveness and versatility of the methods, including for example: controlled increase of the in charge states produced; operation in a dual metal-gaseous ion species mode; very large area beam formation; macroparticle filtering; and the development of processing regimes for optimizing adhesion, morphology and structure. These complementary ion processing techniques provide the plasma tools for doing ion surface modification over a very wide parameter regime, from pure ion implantation at energies approaching the MeV level, through ion mixing at energies in the ∼1 to ∼100 keV range, to IBAD-like processing at energies from a few tens of eV to a few keV. Here the authors review the methods, describe a number of recent developments, and outline some of the surface modification applications to which the methods have been put. 54 refs., 9 figs

Rotation and solvation of ammonium ion

International Nuclear Information System (INIS)

Perrin, C.L.; Gipe, R.K.

1987-01-01

From nitrogen-15 spin-lattice relaxation times and nuclear Overhauser enhancements, the rotational correlations time tau/sub c/ for 15 NH 4 + was determined in s series of solvents. Values of tau/sub c/ range from 0.46 to 20 picoseconds. The solvent dependent of tau/sub c/ cannot be explained in terms of solvent polarity, molecular dipole moment, solvent basicity, solvent dielectric relaxation, or solvent viscosity. The rapid rotation and the variation with solvent can be accounted for by a model that involves hydrogen bonding of an NH proton to more than one solvent molecule in a disordered solvation environment. 25 references, 1 table

Corrosion Thermodynamics of Magnesium and Alloys from First Principles as a Function of Solvation

Science.gov (United States)

Limmer, Krista; Williams, Kristen; Andzelm, Jan

Thermodynamics of corrosion processes occurring on magnesium surfaces, such as hydrogen evolution and water dissociation, have been examined with density functional theory (DFT) to evaluate the effect of impurities and dilute alloying additions. The modeling of corrosion thermodynamics requires examination of species in a variety of chemical and electronic states in order to accurately represent the complex electrochemical corrosion process. In this study, DFT calculations for magnesium corrosion thermodynamics were performed with two DFT codes (VASP and DMol3), with multiple exchange-correlation functionals for chemical accuracy, as well as with various levels of implicit and explicit solvation for surfaces and solvated ions. The accuracy of the first principles calculations has been validated against Pourbaix diagrams constructed from solid, gas and solvated charged ion calculations. For aqueous corrosion, it is shown that a well parameterized implicit solvent is capable of accurately representing all but the first coordinating layer of explicit water for charged ions.

Intensity of f-f bands of neodymium chloride alcohol solvates

International Nuclear Information System (INIS)

Bukietynska, K.; Jezowski-Trzebiatowska, B.; Keller, B.

1981-01-01

Recent results revealed that in alcohol solutions of lanthanide chlorides, at least in the case of Eu 3+ and Yb 3+ ions, there exist mixed solvates, i.e. both chloride ions and solvent molecules are present in the Ln 3+ ion first coordination sphere. This conclusion was drawn from an analysis of the charge transfer transitions in the spectra of Eu 3+ and Yb 3+ chlorides in alcohols (methyl, ethyl, n-propyl), where two separate C.T.bands were observed and identified as C.T. transitions from the alcohol molecule and chloride ion to the Ln 3+ ion. In our previous paper we have reported that the energy of the first f-d transition in the Pr 3+ chloride alcohol solvates varied for different alcohols. These data also confirmed our suggestion that alcohol molecules are present in the first coordination sphere of the lanthanide ion. In the work reported here, we have tried to apply the intensity analysis method to the solution spectra of neodymium chloride dissolved in simple aliphatic alcohols like methanol, ethanol and n-propanol. Experimental details are given. Results are presented and discussed. (author)

Ion implantation of metals

International Nuclear Information System (INIS)

Dearnaley, G.

1976-01-01

In this part of the paper descriptions are given of the effects of ion implantation on (a) friction and wear in metals; and (b) corrosion of metals. In the study of corrosion, ion implantation can be used either to introduce a constituent that is known to convey corrosion resistance, or more generally to examine the parameters which control corrosion. (U.K.)

Enhanced free energy of extraction of Eu3+ and Am3+ ions towards diglycolamide appended calix[4]arene: insights from DFT-D3 and COSMO-RS solvation models.

Science.gov (United States)

Ali, Sk Musharaf

2017-08-22

Density functional theory in conjunction with COSMO and COSMO-RS solvation models employing dispersion correction (DFT-D3) has been applied to gain an insight into the complexation of Eu 3+ /Am 3+ with diglycolamide (DGA) and calix[4]arene appended diglycolamide (CAL4DGA) in ionic liquids by studying structures, energetics, thermodynamics and population analysis. The calculated Gibbs free energy for both Eu 3+ and Am 3+ ions with DGA was found to be smaller than that with CAL4DGA. The entropy of complexation was also found to be reduced to a large extent with DGA compared to complexation with CAL4DGA. The solution phase free energy was found to be negative and was higher for Eu 3+ ion. The entropy of complexation was not only found to be further reduced but also became negative in the case of DGA alone. Though the entropy was found to be negative it could not outweigh the high negative enthalpic contribution. The same trend was observed in the solution where the free energy of extraction, ΔG, for Eu 3+ ions was shown to be higher than that for Am 3+ ions towards free DGA. But the values of ΔG and ΔΔG(= ΔG Eu -ΔG Am ) were found to be much higher with CAL4DGA (-12.58 kcal mol -1 ) in the presence of nitrate ions compared to DGA (-1.69 kcal mol -1 ) due to enhanced electronic interaction and positive entropic contribution. Furthermore, both the COSMO and COSMO-RS models predict very close values of ΔΔΔG (= ΔΔG CAL4DGA - ΔΔG nDGA ), indicating that both solvation models could be applied for evaluating the metal ion selectivity. The value of the reaction free energy was found to be higher after dispersion correction. The charge on the Eu and Am atoms for the complexes with DGA and CAL4DGA indicates the charge-dipole type interaction leading to strong binding energy. The present theoretical results support the experimental findings and thus might be of importance in the design of functionalized ligands.

Solvation of the fluorine containing anions and their lithium salts in propylene carbonate and dimethoxyethane.

Science.gov (United States)

Chaban, Vitaly

2015-07-01

Electrolyte solutions based on the propylene carbonate (PC)-dimethoxyethane (DME) mixtures are of significant importance and urgency due to emergence of lithium-ion batteries. Solvation and coordination of the lithium cation in these systems have been recently attended in detail. However, analogous information concerning anions (tetrafluoroborate, hexafluorophosphate) is still missed. This work reports PM7-MD simulations (electronic-structure level of description) to include finite-temperature effects on the anion solvation regularities in the PC-DME mixture. The reported result evidences that the anions appear weakly solvated. This observation is linked to the absence of suitable coordination sites in the solvent molecules. In the concentrated electrolyte solutions, both BF4(-) and PF6(-) prefer to exist as neutral ion pairs (LiBF4, LiPF6).

Cluster expansion of the solvation free energy difference: Systematic improvements in the solvation of single ions

Science.gov (United States)

Pliego, Josefredo R.

2017-07-01

The cluster expansion method has been used in the imperfect gas theory for several decades. This paper proposes a cluster expansion of the solvation free energy difference. This difference, which results from a change in the solute-solvent potential energy, can be written as the logarithm of a finite series. Similar to the Mayer function, the terms in the series are related to configurational integrals, which makes the integrand relevant only for configurations of the solvent molecules close to the solute. In addition, the terms involve interaction of solute with one, two, and so on solvent molecules. The approach could be used for hybrid quantum mechanical and molecular mechanics methods or mixed cluster-continuum approximation. A simple form of the theory was applied for prediction of pKa in methanol; the results indicated that three explicit methanol molecules and the dielectric continuum lead to a root of mean squared error (RMSE) of only 1.3 pKa units, whereas the pure continuum solvation model based on density method leads to a RMSE of 6.6 pKa units.

Competitive solvation of (bis)(trifluoromethanesulfonyl)imide anion by acetonitrile and water

Science.gov (United States)

Chaban, Vitaly

2014-10-01

Competitive solvation of an ion by two or more solvents is one of the key phenomena determining the identity of our world. Solvation in polar solvents frequently originates from non-additive non-covalent interactions. Pre-parametrized potentials poorly capture these interactions, unless the force field derivation is repeated for every new system. Development cost increases drastically as new chemical species are supplied. This work represents an alternative simulation approach, PM7-MD, by coupling the latest semiempirical parametrization, PM7, with equation-of-motion propagation scheme and temperature coupling. Using a competitive solvation of (bis)(trifluoromethanesulfonyl)imide anion in acetonitrile and water, the work demonstrates efficiency and robustness of PM7-MD.

Minimization of Ion-Solvent Clusters in Gel Electrolytes Containing Graphene Oxide Quantum Dots for Lithium-Ion Batteries.

Science.gov (United States)

Chen, Yen-Ming; Hsu, Shih-Ting; Tseng, Yu-Hsien; Yeh, Te-Fu; Hou, Sheng-Shu; Jan, Jeng-Shiung; Lee, Yuh-Lang; Teng, Hsisheng

2018-03-01

This study uses graphene oxide quantum dots (GOQDs) to enhance the Li + -ion mobility of a gel polymer electrolyte (GPE) for lithium-ion batteries (LIBs). The GPE comprises a framework of poly(acrylonitrile-co-vinylacetate) blended with poly(methyl methacrylate) and a salt LiPF 6 solvated in carbonate solvents. The GOQDs, which function as acceptors, are small (3-11 nm) and well dispersed in the polymer framework. The GOQDs suppress the formation of ion-solvent clusters and immobilize PF6- anions, affording the GPE a high ionic conductivity and a high Li + -ion transference number (0.77). When assembled into Li|electrolyte|LiFePO 4 batteries, the GPEs containing GOQDs preserve the battery capacity at high rates (up to 20 C) and exhibit 100% capacity retention after 500 charge-discharge cycles. Smaller GOQDs are more effective in GPE performance enhancement because of the higher dispersion of QDs. The minimization of both the ion-solvent clusters and degree of Li + -ion solvation in the GPEs with GOQDs results in even plating and stripping of the Li-metal anode; therefore, Li dendrite formation is suppressed during battery operation. This study demonstrates a strategy of using small GOQDs with tunable properties to effectively modulate ion-solvent coordination in GPEs and thus improve the performance and lifespan of LIBs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solvation numbers and hydration constant for thorium(IV) in ethanol-water medium

International Nuclear Information System (INIS)

Sedaira, H.; Idriss, K.A.; Hashem, E.Y.

1996-01-01

The solvation number and hydration constant of Th 4+ in ethanol-water medium were determined at 25 degrees C using UV-spectral and electrochemical measurements. A solvate formation equilibrium is demonstrated and characterized. Three molecules of ethanol (S) can bond to the metal cation with strengths comparable to that for H 2 O to form ThS 3 (H 2 O) 3 4+ . Formation of thorium monochelate with lawsone (2-hydroxy-1.4-naphthoquinone) eliminates bonding with alcohol molecules. The dissociation constant of the chelating agent s K a and the formation contant of the monochelated metal ion s K f * that are essentially independent of the solution composition are evaluated. Hydration titrations involving thorium-lawsone monochlate are performed and the data obtained from the changes of pH with solvent composition are analyzed. The solution independent constant, s K f * for thorium-lawsone complex formation in mixed aqueous ethanol is given by log x K f * =vpK a + log s K h - log [LH] - vpH + 3 log v where vpK a is the dissociation constant of the chelating agent LH in the solvent system of v volume fraction of water and s K h is the solution-independent hydration constant of thorium (IV) in the solvent system. Log-values for the constants s K h , s K f * and s K z * are found to be 7.8 ±0.02, 11.38±0.04 and -0.753, respectively

Preferential solvation: dividing surface vs excess numbers.

Science.gov (United States)

Shimizu, Seishi; Matubayasi, Nobuyuki

2014-04-10

How do osmolytes affect the conformation and configuration of supramolecular assembly, such as ion channel opening and actin polymerization? The key to the answer lies in the excess solvation numbers of water and osmolyte molecules; these numbers are determinable solely from experimental data, as guaranteed by the phase rule, as we show through the exact solution theory of Kirkwood and Buff (KB). The osmotic stress technique (OST), in contrast, purposes to yield alternative hydration numbers through the use of the dividing surface borrowed from the adsorption theory. However, we show (i) OST is equivalent, when it becomes exact, to the crowding effect in which the osmolyte exclusion dominates over hydration; (ii) crowding is not the universal driving force of the osmolyte effect (e.g., actin polymerization); (iii) the dividing surface for solvation is useful only for crowding, unlike in the adsorption theory which necessitates its use due to the phase rule. KB thus clarifies the true meaning and limitations of the older perspectives on preferential solvation (such as solvent binding models, crowding, and OST), and enables excess number determination without any further assumptions.

Engineering of microorganisms towards recovery of rare metal ions

Energy Technology Data Exchange (ETDEWEB)

Kuroda, Kouichi; Ueda, Mitsuyoshi [Kyoto Univ. (Japan). Div. of Applied Life Sciences

2010-06-15

The bioadsorption of metal ions using microorganisms is an attractive technology for the recovery of rare metal ions as well as removal of toxic heavy metal ions from aqueous solution. In initial attempts, microorganisms with the ability to accumulate metal ions were isolated from nature and intracellular accumulation was enhanced by the overproduction of metal-binding proteins in the cytoplasm. As an alternative, the cell surface design of microorganisms by cell surface engineering is an emerging strategy for bioadsorption and recovery of metal ions. Cell surface engineering was firstly applied to the construction of a bioadsorbent to adsorb heavy metal ions for bioremediation. Cell surface adsorption of metal ions is rapid and reversible. Therefore, adsorbed metal ions can be easily recovered without cell breakage, and the bioadsorbent can be reused or regenerated. These advantages are suitable for the recovery of rare metal ions. Actually, the cell surface display of a molybdate-binding protein on yeast led to the enhanced adsorption of molybdate, one of the rare metal ions. An additional advantage is that the cell surface display system allows high-throughput screening of protein/peptide libraries owing to the direct evaluation of the displayed protein/peptide without purification and concentration. Therefore, the creation of novel metal-binding protein/ peptide and engineering of microorganisms towards the recovery of rare metal ions could be simultaneously achieved. (orig.)

Solvation structure determination of nickel(II) ion in six nitriles using extended X-ray absorption fine structure spectroscopy

International Nuclear Information System (INIS)

Inada, Yasuhiro; Funahashi, Shigenobu

1997-01-01

The solvation structures of the nickel(II) ion in six nitriles have been determined using X-ray absorption fine structure spectroscopy. The coordination number and the Ni-N bond length are 6 and 206.9 ± 0.6 pm in acetonitrile, 5.9 ± 0.2 and 206.9 ± 0.6 pm in propionitrile, 6.0 ± 0.2 and 206.8 ± 0.6 pm in butyronitrile, 6.0 ± 0.2 and 206.8 ± 0.6 pm in isobutyronitrile, 6.0 ± 0.2 and 206.8 ± 0.6 pm in valeronitrile, and 6.0 ± 0.2 and 206.5 ± 0.7 pm in benzonitrile, respectively. The structure parameters around the nickel(II) ion in all the nitriles are not affected by the bulkiness of the nitrile molecules. On the basis of the obtained structure parameters, we have discussed the structural characteristics around the nickel(II) ion with nitrogen and oxygen donor solvents and the reaction mechanisms for nitrile exchange on the nickel(II) ion. (author)

Versatile high current metal ion implantation facility

International Nuclear Information System (INIS)

Brown, I.G.; Dickinson, M.R.; Galvin, J.E.; Godechot, X.; MacGill, R.A.

1992-01-01

A metal ion implantation facility has been developed with which high current beams of practically all the solid metals of the periodic table can be produced. A multicathode, broad-beam, metal vapor vacuum arc ion source is used to produce repetitively pulsed metal ion beams at an extraction voltage of up to 100 kV, corresponding to an ion energy of up to several hundred kiloelectronvolts because of the ion charge state multiplicity, and with a beam current of up to several amps peak pulsed and several tens of milliamps time averaged delivered onto a downstream target. Implantation is done in a broad-beam mode, with a direct line of sight from ion source to target. Here we summarize some of the features of the ion source and the implantation facility that has been built up around it. (orig)

Ion association thermodynamics of alkali metal tetraphenylborates in the mixed solvent propylenecarbonate-1,2-dimethoxyethane

International Nuclear Information System (INIS)

Fialkov, Yu.Ya.; Gorbachev, V.Yu.

1997-01-01

Polythermal dependences of constants of ion association of (Li + -Cs + )BPh 4 salts in mixed solvent differ significantly in permittivity. Thermodynamic characteristics of this process are calculated and their relation with solvation processes is analyzed. (author)

Coprecipitation of alkali metal ions with calcium carbonate

International Nuclear Information System (INIS)

Okumura, Minoru; Kitano, Yasushi

1986-01-01

The coprecipitation of alkali metal ions Li + , Na + , K + and Rb + with calcium carbonate has been studied experimentally and the following results have been obtained: (1) Alkali metal ions are more easily coprecipitated with aragonite than with calcite. (2) The relationship between the amounts of alkali metal ions coprecipitated with aragonite and their ionic radii shows a parabolic curve with a peak located at Na + which has approximately the same ionic radius as Ca 2+ . (3) However, the amounts of alkali metal ions coprecipitated with calcite decrease with increasing ionic radius of alkali metals. (4) Our results support the hypothesis that (a) alkali metals are in interstitial positions in the crystal structure of calcite and do not substitute for Ca 2+ in the lattice, but (b) in aragonite, alkali metals substitute for Ca 2+ in the crystal structure. (5) Magnesium ions in the parent solution increase the amounts of alkali metal ions (Li + , Na + , K + and Rb + ) coprecipitated with calcite but decrease those with aragonite. (6) Sodium-bearing aragonite decreases the incorporation of other alkali metal ions (Li + , K + and Rb + ) into the aragonite. (author)

Solvation of a Small Metal-Binding Peptide in Room-Temperature Ionic Liquids

Energy Technology Data Exchange (ETDEWEB)

Shim, Youngseon; Jung, Younjoon [Seoul National Univ., Seoul (Korea, Republic of); Kim, Hyung J. [Carnegie Mellon Univ., Pittsburgh (United States)

2012-11-15

Structural properties of a small hexapeptide molecule modeled after metal-binding siderochrome immersed in a room-temperature ionic liquid (RTIL) are studied via molecular dynamics simulations. We consider two different RTILs, each of which is made up of the same cationic species, 1-butyl-3-methylimidazolium (BMI{sup +}), but different anions, hexafluorophosphate (PF{sub 6}{sup -}) and chloride (Cl{sup -}). We investigate how anionic properties such as hydrophobicity/hydrophilicity or hydrogen bonding capability affect the stabilization of the peptide in RTILs. To examine the effect of peptide-RTIL electrostatic interactions on solvation, we also consider a hypothetical solvent BMI{sup 0}Cl{sup 0}, a non-ionic counter-part of BMI{sup +}Cl{sup -}. For reference, we investigate solvation structures in common polar solvents, water and dimethylsulfoxide (DMSO). Comparison of BMI{sup +}Cl{sup -} and BMI{sup 0}Cl{sup 0} shows that electrostatic interactions of the peptide and RTIL play a significant role in the conformational fluctuation of the peptide. For example, strong electrostatic interactions between the two favor an extended conformation of the peptide by reducing its structural fluctuations. The hydrophobicity/hydrophilicity of RTIL anions also exerts a notable influence; specifically, structural fluctuations of the peptide become reduced in more hydrophilic BMI{sup +}Cl{sup -}, compared with those in more hydrophobic BMI{sup +}PF{sub 6}{sup -}. This is ascribed to the good hydrogen-bond accepting power of chloride anions, which enables them to bind strongly to hydroxyl groups of the peptide and to stabilize its structure. Transport properties of the peptide are examined briefly. Translations of the peptide significantly slow down in highly viscous RTILs.

Metal vapor vacuum arc ion sources

International Nuclear Information System (INIS)

Brown, I.G.; Dickinson, M.R.; Galvin, J.E.; Godechot, X.; MacGill, R.A.

1990-06-01

We have developed a family of metal vapor vacuum are (MEVVA) high current metal ion sources. The sources were initially developed for the production of high current beams of metal ions for heavy ion synchrotron injection for basic nuclear physics research; more recently they have also been used for metal ion implantation. A number of different embodiments of the source have been developed for these specific applications. Presently the sources operate in a pulsed mode, with pulse width of order 1 ms and repetition rate up to 100 pps. Beam extraction voltage is up to 100 kV, and since the ions produced in the vacuum arc plasma are in general multiply ionized the ion energy is up to several hundred keV. Beam current is up to several Amperes peak and around 10 mA time averaged delivered onto target. Nearly all of the solid metals of the Periodic Table have been use to produce beam. A number of novel features have been incorporated into the sources, including multiple cathodes and the ability to switch between up to 18 separate cathode materials simply and quickly, and a broad beam source version as well as miniature versions. here we review the source designs and their performance. 45 refs., 7 figs

Novel metal ion surface modification technique

International Nuclear Information System (INIS)

Brown, I.G.; Godechot, X.; Yu, K.M.

1990-10-01

We describe a method for applying metal ions to the near-surface region of solid materials. The added species can be energetically implanted below the surface or built up as a surface film with an atomically mixed interface with the substrate; the metal ion species can be the same as the substrate species or different from it, and more than one kind of metal species can be applied, either simultaneously or sequentially. Surface structures can be fabricated, including coatings and thin films of single metals, tailored alloys, or metallic multilayers, and they can be implanted or added onto the surface and ion beam mixed. We report two simple demonstrations of the method: implantation of yttrium into a silicon substrate at a mean energy of 70 keV and a dose of 1 x 10 16 atoms/cm 2 , and the formation of a titanium-yttrium multilayer structure with ion beam mixing to the substrate. 17 refs., 3 figs

Metallic vapor supplying by the electron bombardment for a metallic ion production with an ECR ion source

Energy Technology Data Exchange (ETDEWEB)

Kitagawa, Atsushi; Sasaki, Makoto; Muramatsu, Masayuki [National Inst. of Radiological Sciences, Chiba (Japan); Jincho, Kaoru; Sasaki, Noriyuki; Sakuma, Tetsuya; Takasugi, Wataru; Yamamoto, Mitsugu [Accelerator Engineering Corporation, Chiba (Japan)

2001-11-19

To produce the metallic ion beam for the injection into the Heavy Ion Medical Accelerator in Chiba (HIMAC) at the National Institute of Radiological Sciences (NIRS), a new gas supply method has been developed for an 18 GHz ECR ion source (NIRS-HEC). A metallic target rod at a high positive potential is melted by the electron bombardment technique. The evaporated gas with a maximum flow rate of 50A/sec is supplied into the ECR plasma in case of Fe metal. (author)

Metallic vapor supplying by the electron bombardment for a metallic ion production with an ECR ion source

International Nuclear Information System (INIS)

Kitagawa, Atsushi; Sasaki, Makoto; Muramatsu, Masayuki; Jincho, Kaoru; Sasaki, Noriyuki; Sakuma, Tetsuya; Takasugi, Wataru; Yamamoto, Mitsugu

2001-01-01

To produce the metallic ion beam for the injection into the Heavy Ion Medical Accelerator in Chiba (HIMAC) at the National Institute of Radiological Sciences (NIRS), a new gas supply method has been developed for an 18 GHz ECR ion source (NIRS-HEC). A metallic target rod at a high positive potential is melted by the electron bombardment technique. The evaporated gas with a maximum flow rate of 50A/sec is supplied into the ECR plasma in case of Fe metal. (author)

Molecular dynamics study of thermodynamic stability and dynamics of [Li(glyme)]+ complex in lithium-glyme solvate ionic liquids

Science.gov (United States)

Shinoda, Wataru; Hatanaka, Yuta; Hirakawa, Masashi; Okazaki, Susumu; Tsuzuki, Seiji; Ueno, Kazuhide; Watanabe, Masayoshi

2018-05-01

Equimolar mixtures of glymes and organic lithium salts are known to produce solvate ionic liquids, in which the stability of the [Li(glyme)]+ complex plays an important role in determining the ionic dynamics. Since these mixtures have attractive physicochemical properties for application as electrolytes, it is important to understand the dependence of the stability of the [Li(glyme)]+ complex on the ion dynamics. A series of microsecond molecular dynamics simulations has been conducted to investigate the dynamic properties of these solvate ionic liquids. Successful solvate ionic liquids with high stability of the [Li(glyme)]+ complex have been shown to have enhanced ion dynamics. Li-glyme pair exchange rarely occurs: its characteristic time is longer than that of ion diffusion by one or two orders of magnitude. Li-glyme pair exchange most likely occurs through cluster formation involving multiple [Li(glyme)]+ pairs. In this process, multiple exchanges likely take place in a concerted manner without the production of energetically unfavorable free glyme or free Li+ ions.

Ion-beam-mixing in metal-metal systems and metal-silicon systems

International Nuclear Information System (INIS)

Hung, L.

1984-01-01

The influence of energetic ion bombardment on the composition and structure of thin film materials and utilization of ion-beam-mixing techniques to modify interfacial reactions are reported in this thesis. The phase formation in metals by using ion mixing techniques has been studied. Upon ion irradiation of Al/Pt, Al/Pd and Al/Ni thin films, only the simplest intermetallic compounds of PdAl and NiAl were formed in crystalline structure, while the amorphous phase has been observed over a large range of composition. Ion mixing of Au/Cu bilayers resulted in the formation of substitutional solid solutions with no trace of ordered compounds. The formation of the ordered compound CuAu was achieved either by irradiation of bilayers with Ar ions at elevated substrate temperature or by irradiation of the mixed layers with He ions at relatively low temperature. In the Au/Al system several crystal compounds existed in the as-deposited samples. These phases remained crystalline or transformed into other equilibrium compounds upon ion irradiation. The results suggest that the phase formation by ion mixing is dependent on the high quench rate in the collision cascade region and the atomic mobility at the irradiation temperature. The argument can be applied to silicide forming systems. With near-noble metals, the mixed atoms are mobile and form metallurgically distinct phases. With refractory metals, amorphous phases are formed due to lack of atomic mobility

High charge state metal ion production in vacuum arc ion sources

International Nuclear Information System (INIS)

Brown, I.G.; Anders, A.; Anders, S.

1994-01-01

The vacuum arc is a rich source of highly ionized metal plasma that can be used to make a high current metal ion source. Vacuum arc ion sources have been developed for a range of applications including ion implantation for materials surface modification, particle accelerator injection for fundamental nuclear physics research, and other fundamental and applied purposes. Typically the source is repetitively pulsed with pulse length of order a millisecond and duty cycle or order 1% and operation of a dc embodiment has been demonstrated also. Beams have been produced from over 50 of the solid metals of the periodic table, with mean ion energy up to several hundred keV and with peak (pulsed) beam current up to several amperes. The ion charge state distribution has been extensively studied. Ion spectra have been measured for a wide range of metallic cathode materials, including Li, C, Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ge, Sr, Y, Zr, Nb, Mo, Pd, Ag, Cd, In, Sn, Sb, Ba, La, Ce, Pr, Nd, Sm, Gd, Dy, Ho, Er, Tm, Yb, Hf, Ta, W, Ir, Pt, Au, Pb, Bi, Th and U, as well as compound and alloy cathode materials such as TiC, SiC, UC, PbS, brass, and stainless steel. The ions generated are in general multiply-stripped with a mean charge state of from 1 to 3, depending on the particular metal species, and the charge state distribution can have components from Q = 1+ to 6+. Here the authors review the characteristics of vacuum arc ion sources from the perspective of their high charge state metal ion production

The dynamics of Ca2+ ions within the solvation shell of calbindin D9k.

Directory of Open Access Journals (Sweden)

Elad Project

Full Text Available The encounter of a Ca(2+ ion with a protein and its subsequent binding to specific binding sites is an intricate process that cannot be fully elucidated from experimental observations. We have applied Molecular Dynamics to study this process with atomistic details, using Calbindin D9k (CaB as a model protein. The simulations show that in most of the time the Ca(2+ ion spends within the Debye radius of CaB, it is being detained at the 1st and 2nd solvation shells. While being detained near the protein, the diffusion coefficient of the ion is significantly reduced. However, due to the relatively long period of detainment, the ion can scan an appreciable surface of the protein. The enhanced propagation of the ion on the surface has a functional role: significantly increasing the ability of the ion to scan the protein's surface before being dispersed to the bulk. The contribution of this mechanism to Ca(2+ binding becomes significant at low ion concentrations, where the intervals between successive encounters with the protein are getting longer. The efficiency of the surface diffusion is affected by the distribution of charges on the protein's surface. Comparison of the Ca(2+ binding dynamics in CaB and its E60D mutant reveals that in the wild type (WT protein the carboxylate of E60 function as a preferred landing-site for the Ca(2+ arriving from the bulk, followed by delivering it to the final binding site. Replacement of the glutamate by aspartate significantly reduced the ability to transfer Ca(2+ ions from D60 to the final binding site, explaining the observed decrement in the affinity of the mutated protein to Ca(2+.

Adsorption of heavy metal ions on different clays

International Nuclear Information System (INIS)

Kruse, K.

1992-01-01

The aim of the present dissertation is to study the adsorption of heavy metal ions (Cd 2+ , Cu 2+ , Pb 2+ , Zn 2+ ) and their mixtures on clays. Different clays and bentonites (Ca 2+ -bentonite, activated Na + -bentonite, special heavy metal adsorber bentonite, two organophilic bentonites and a mixed layer clay) were used. The adsorbed metal ions were desorbed by appropriate solutions of HCl, EDTA and dioctadecyl dimethylammonium bromide. High concentrations of the heavy metal ions in the solutions can be reached. The desorption guarantees economical recycling. After desorption the clays were used (up to three times) for purification of contaminated water. The best experimental conditions, i.e. the highest adsorption of heavy metal ions from aqueous solutions was found for the greatest ratio of adsorbent/adsorbate. The adsorption was very fast. Calcium, sodium bentonites and the heavy metal adsorber bentonite attained the highest adsorption and desorption for Cu 2+, Zn 2+ and Pb 2+ ions. Cd 2+ ions were only absorbed by Silitonit, a special heavy metal absorber bentonite. The mixed layer clay (Opalit) ranges in adsorption and desorption properties below the unmodified Ca 2+ -bentonite (Montigel) or the activated Na + -bentonite. Only Tixosorb and Tixogel (organophilic bentonites) reach the lowest value of heavy metal adsorption. Only lead cations which are characterised by good polarizability were adsorbed at higher rates, therefore the organophilic bentonites are not appropriate for adsorption of heavy metal ions from aqueous solutions. Mixing of the metal ions generally decreases the adsorption of Pb 2+ and increases the adsorption of Cd 2+ . From mixtures if heavy metal ions adsorption and desorption of Cu 2+ ions reached a maximum for all clays. (author) figs., tabs., 56 refs

Selective solvation extraction of gold from alkaline cyanide solution by alkyl phosphorus esters

Energy Technology Data Exchange (ETDEWEB)

Miller, J.D.; Wan, R.Y.; Mooiman, M.B.; Sibrell, P.L.

1987-01-01

Research efforts have shown that solvation extraction of gold from alkaline cyanide solution is possible by alkyl phosphorus esters. Both tributyl phosphate (TBP) and dibutyl butyl phosphonate (DBBP) appear to be effective extractants for gold and exhibit high loading capacities exceeding 30 gpl. Selective solvation extraction of gold from alkaline cyanide solution can be achieved with selectivity factors relative to other cyanoanions as high as 1000 under certain circumstances. Variables influencing the selectivity such as ionic strength, temperature, and extractant structure, are discussed in terms of the extraction chemistry, which seems to involve the solvation of a M dot, dot, dot Au(CN)2 ion pair.

Laccase Immobilization by Chelated Metal Ion Coordination Chemistry

Directory of Open Access Journals (Sweden)

Qingqing Wang

2014-09-01

Full Text Available In this work, amidoxime polyacrylonitrile (AOPAN nanofibrous membrane was prepared by a reaction between PAN nanofibers and hydroxylamine hydrochloride. The AOPAN nanofibrous membranes were used for four metal ions (Fe3+, Cu2+, Ni2+, Cd2+ chelation under different conditions. Further, the competition of different metal ions coordinating with AOPAN nanofibrous membrane was also studied. The AOPAN chelated with individual metal ion (Fe3+, Cu2+, Ni2+, Cd2+ and also the four mixed metal ions were further used for laccase (Lac immobilization. Compared with free laccase, the immobilized laccase showed better resistance to pH and temperature changes as well as improved storage stability. Among the four individual metal ion chelated membranes, the stability of the immobilized enzymes generally followed the order as Fe–AOPAN–Lac > Cu–AOPAN–Lac > Ni–AOPAN–Lac > Cd–AOPAN–Lac. In addition, the immobilized enzyme on the carrier of AOPAN chelated with four mixed metal ions showed the best properties.

Metallic ion release from biocompatible cobalt-based alloy

Directory of Open Access Journals (Sweden)

Dimić Ivana D.

2014-01-01

Full Text Available Metallic biomaterials, which are mainly used for the damaged hard tissue replacements, are materials with high strength, excellent toughness and good wear resistance. The disadvantages of metals as implant materials are their susceptibility to corrosion, the elastic modulus mismatch between metals and human hard tissues, relatively high density and metallic ion release which can cause serious health problems. The aim of this study was to examine metallic ion release from Co-Cr-Mo alloy in artificial saliva. In that purpose, alloy samples were immersed into artificial saliva with different pH values (4.0, 5.5 and 7.5. After a certain immersion period (1, 3 and 6 weeks the concentrations of released ions were determined using Inductively Coupled Plasma - Mass Spectrophotometer (ICP-MS. The research findings were used in order to define the dependence between the concentration of released metallic ions, artificial saliva pH values and immersion time. The determined released metallic ions concentrations were compared with literature data in order to describe and better understand the phenomenon of metallic ion release from the biocompatible cobalt-based alloy. [Projekat Ministarstva nauke Republike Srbije, br. III 46010 i br. ON 174004

Solvation thermodynamics

CERN Document Server

Ben-Naim, Arieh

1987-01-01

This book deals with a subject that has been studied since the beginning of physical chemistry. Despite the thousands of articles and scores of books devoted to solvation thermodynamics, I feel that some fundamen­ tal and well-established concepts underlying the traditional approach to this subject are not satisfactory and need revision. The main reason for this need is that solvation thermodynamics has traditionally been treated in the context of classical (macroscopic) ther­ modynamics alone. However, solvation is inherently a molecular pro­ cess, dependent upon local rather than macroscopic properties of the system. Therefore, the starting point should be based on statistical mechanical methods. For many years it has been believed that certain thermodynamic quantities, such as the standard free energy (or enthalpy or entropy) of solution, may be used as measures of the corresponding functions of solvation of a given solute in a given solvent. I first challenged this notion in a paper published in 1978 b...

On the coupling between molecular diffusion and solvation shell exchange

DEFF Research Database (Denmark)

Møller, Klaus Braagaard; Rey, Rossend; Masia, Marco

2005-01-01

The connection between diffusion and solvent exchanges between first and second solvation shells is studied by means of molecular dynamics simulations and analytic calculations, with detailed illustrations for water exchange for the Li+ and Na+ ions, and for liquid argon. First, two methods...

Metallic ions in the upper atmosphere

International Nuclear Information System (INIS)

Kumar, S.

1979-01-01

During the past 20 years considerable progress has been made in establishing the presence of metallic ions in the sporadic E layers at mid latitudes and as discrete patches at high altitudes in the equatorial ionosphere. The E-region observations have been based on rocket flights, which represent local conditions faithfully. But the global distribution of metallic ions and variations relating to changes in season, local time, magnetic activity, etc., which require satellite data, have been largely unexamined. This work presents a few aspects of this missing global distribution over an altitude range of 100 to 1000 km, using the data from AE-C, AE-D, and OGO-6 satellites and the rocket flights 18.117 and 18.118 from Wallops Island on July 12 and 13, 1971. The rocket data provide a day-night pair of vertical profiles that include altitudes not covered by the satellites. Results are presented for Mg + , Al + , Si + and Fe + ions in terms of their detection probabilities, median concentrations and relative abundances with respect to Mg + ions as a function of significant geophysical parameters. Na + and K + ions have been excluded from this study because alkali metal ions driven off the spacecraft hamper the measurement of ambient Na + and K + ions. This study has indicated that in general different metallic ions appear together in comparable concentrations except for Al + , which is an order of magnitude smaller than the others

Solubility and solvation of alkali metal perchlorates, tetramethyl and tetraethylammonium in aqua-ketone solvents

International Nuclear Information System (INIS)

Kireev, A.A.; Pak, T.G.; Bezuglyj, V.D.

1998-01-01

The KClO 4 , RbClO 4 , CsClO 4 , (CH 3 ) 4 NClO 4 , (C 2 H 5 ) 4 NClO 4 solubility in water and water-acetone, water-methylethylketone mixtures is determined through the method of isothermal saturation at 298.15 K. Dissociation constants of alkali metals perchlorates in acetone and its 90% mixtures (by volume) are determined conductometrically. Solubility products and standard energies of the Gibbs transfer of the studied electrolytes from water into water-acetone and water-methylethylketone solvents. It is established that the Gibbs standard energies of Na + , K + , Rb + and Cs + cations transfer from water to water-ketone solvents are close to each other. It is shown that the effect of acetone and methylethylketone on solvation of the studied electrolytes is practically similar

Comparison of molecular mechanics-Poisson-Boltzmann surface area (MM-PBSA) and molecular mechanics-three-dimensional reference interaction site model (MM-3D-RISM) method to calculate the binding free energy of protein-ligand complexes: Effect of metal ion and advance statistical test

Science.gov (United States)

Pandey, Preeti; Srivastava, Rakesh; Bandyopadhyay, Pradipta

2018-03-01

The relative performance of MM-PBSA and MM-3D-RISM methods to estimate the binding free energy of protein-ligand complexes is investigated by applying these to three proteins (Dihydrofolate Reductase, Catechol-O-methyltransferase, and Stromelysin-1) differing in the number of metal ions they contain. None of the computational methods could distinguish all the ligands based on their calculated binding free energies (as compared to experimental values). The difference between the two comes from both polar and non-polar part of solvation. For charged ligand case, MM-PBSA and MM-3D-RISM give a qualitatively different result for the polar part of solvation.

Ultrafast electron dynamics at alkali/ice structures adsorbed on a metal surface

International Nuclear Information System (INIS)

Meyer, Michael

2011-01-01

The goal of this work is to study the interaction between excess electrons in water ice structures adsorbed on metal surfaces and other charged or neutral species, like alkali ions, or chemically reactive molecules, like chlorofluorocarbons (CFC), respectively. The excess electrons in the ice can interact with the ions directly or indirectly via the hydrogen bonded water molecules. In both cases the presence of the alkali influences the population, localization, and lifetime of electronic states of excess electrons in the ice adlayer. These properties are of great relevance when considering the highly reactive character of the excess electrons, which can mediate chemical reactions by dissociative electron attachment (DEA). The influence of alkali adsorption on electron solvation and transfer dynamics in ice structures is investigated for two types of adsorption configurations using femtosecond time-resolved two-photon photoelectron spectroscopy. In the first system alkali atoms are coadsorbed on top of a wetting amorphous ice film adsorbed on Cu(111). At temperatures between 60 and 100 K alkali adsorption leads to the formation of positively charged alkali ions at the ice/vacuum interface. The interaction between the alkali ions at the surface and the dipole moments of the surrounding water molecules results in a reorientation of the water molecules. As a consequence new electron trapping sites, i.e. at local potential minima, are formed. Photoinjection of excess electrons into these alkali-ion covered amorphous ice layers, results in the trapping of a solvated electron at an alkali-ion/water complex. In contrast to solvation in pure amorphous ice films, where the electrons are located in the bulk of the ice layer, solvated electrons at alkali-ion/water complexes are located at the ice/vacuum interface. They exhibit lifetimes of several picoseconds and show a fast energetic stabilization. With ongoing solvation, i.e. pump-probe time delay, the electron transfer is

Analysis of metal ion release from biomedical implants

Directory of Open Access Journals (Sweden)

Ivana Dimić

2013-06-01

Full Text Available Metallic biomaterials are commonly used for fixation or replacement of damaged bones in the human body due to their good combination of mechanical properties. The disadvantage of metals as implant materials is their susceptibility to corrosion and metal ion release, which can cause serious health problems. In certain concentrations metals and metal ions are toxic and their presence can cause diverse inflammatory reactions, genetic mutations or even cancer. In this paper, different approaches to metal ion release examination, from biometallic materials sample preparation to research results interpretation, will be presented. An overview of the analytical techniques, used for determination of the type and concentration of released ions from implants in simulated biofluids, is also given in the paper.

Multiple time step molecular dynamics in the optimized isokinetic ensemble steered with the molecular theory of solvation: Accelerating with advanced extrapolation of effective solvation forces

International Nuclear Information System (INIS)

Omelyan, Igor; Kovalenko, Andriy

2013-01-01

steered by effective solvation forces allows huge outer time steps up to tens of picoseconds without affecting the equilibrium and conformational properties, and thus provides a 100- to 500-fold effective speedup in comparison to conventional MD with explicit solvent. With the statistical-mechanical 3D-RISM-KH account for effective solvation forces, the method provides efficient sampling of biomolecular processes with slow and/or rare solvation events such as conformational transitions of hydrated alanine dipeptide with the mean life times ranging from 30 ps up to 10 ns for “flip-flop” conformations, and is particularly beneficial for biomolecular systems with exchange and localization of solvent and ions, ligand binding, and molecular recognition

Silver atom solvation and desolvation in ice matrices: study of solvation shell geometry by electron spin resonance and electron spin echo methods

Energy Technology Data Exchange (ETDEWEB)

Kevan, L; Narayana, P A

1978-01-01

Results of studies of the solvation shell structure of silver atoms in ice matrix at 4/sup 0/K by electron spin resonance (ESR) and electron spin echo spectrometry are reported. Drastic change in the hyperfine coupling constant of the silver atom was noted when the silver atom initially produced at 4/sup 0/K was warmed to 77/sup 0/K and reexamined by ESR at 4/sup 0/K. This suggested a very drastic rearrangement of the water molecules surrounding the silver atom. The geometric arrangement of water molecules around the silver atom produced at 4/sup 0/K was what would be expected for a solvated silver ion, indicating that no rearrangement had occurred after the silver atom formed. The addition of a little thermal excitation (heating to 77/sup 0/K) results in the geometry changes than can be explained by assuming either that a water molecule rotates around one of its OH bands or by the development of a hydrogen bond between the silver atom and one of the first solvation shell water molecules. Optical excitation in the absorption band of the silver atom in the ice matrix at 400nm resulted in desolvation of the silver ion or a reversion to the structure originally obtained by reaction of solver salts in ic matrix with radiation produced electrons. This was best explained by a charge transfer mechanism. (BLM)

Noble metal extraction and sorption concentrating

International Nuclear Information System (INIS)

Petrukhin, O.M.; Malofeeva, G.I.

1985-01-01

Works performed in the USSR Academy of Sciences GEOCHI laboratory of extraction methods and devoted to selectivity problems of extraction and sorption methods of platinum metal, cadmium and indium concentrating in analytical chemistry are discussed. On choosing complexino. reagent main attention is paid to the selectivity variation based on different stability of metal complexes. Platinum metals are extracted in the form of ion associates when usinq hard, mainly oxyqen-containing, extractants. Coordination-solvated metal complexes are extracted white usinq extractants containing sulfur, trivalent phosphorus and aromatic nitroqen as donor anions. Selectivity is maximum for sulfur- and nitroren-containinq extractants and sorbents. In case of the group extraction of platinum metals sorption is preferable and in case of selective extraction of individual metals, especially, in case of need of relative concentratinq extraction is preferable

Amorphization of metals by ion implantation and ion beam mixing

International Nuclear Information System (INIS)

Rauschenbach, B.; Heera, V.

1988-01-01

Amorphous metallic systems can be formed either by high-fluence ion implantation of glassforming species or by irradiation of layered metal systems with inert gas ions. Both techniques and experimental examples are presented. Empirical rules are discussed which predict whether a given system can be transformed into an amorphous phase. Influence of temperature, implantation dose and pre-existing crystalline metal composition on amorphization is considered. Examples are given of the implantation induced amorphous structure, recrystallization and formation of quasicrystalline structures. (author)

Pseudo ribbon metal ion beam source

International Nuclear Information System (INIS)

Stepanov, Igor B.; Ryabchikov, Alexander I.; Sivin, Denis O.; Verigin, Dan A.

2014-01-01

The paper describes high broad metal ion source based on dc macroparticle filtered vacuum arc plasma generation with the dc ion-beam extraction. The possibility of formation of pseudo ribbon beam of metal ions with the parameters: ion beam length 0.6 m, ion current up to 0.2 A, accelerating voltage 40 kV, and ion energy up to 160 kV has been demonstrated. The pseudo ribbon ion beam is formed from dc vacuum arc plasma. The results of investigation of the vacuum arc evaporator ion-emission properties are presented. The influence of magnetic field strength near the cathode surface on the arc spot movement and ion-emission properties of vacuum-arc discharge for different cathode materials are determined. It was shown that vacuum-arc discharge stability can be reached when the magnetic field strength ranges from 40 to 70 G on the cathode surface

Pseudo ribbon metal ion beam source.

Science.gov (United States)

Stepanov, Igor B; Ryabchikov, Alexander I; Sivin, Denis O; Verigin, Dan A

2014-02-01

The paper describes high broad metal ion source based on dc macroparticle filtered vacuum arc plasma generation with the dc ion-beam extraction. The possibility of formation of pseudo ribbon beam of metal ions with the parameters: ion beam length 0.6 m, ion current up to 0.2 A, accelerating voltage 40 kV, and ion energy up to 160 kV has been demonstrated. The pseudo ribbon ion beam is formed from dc vacuum arc plasma. The results of investigation of the vacuum arc evaporator ion-emission properties are presented. The influence of magnetic field strength near the cathode surface on the arc spot movement and ion-emission properties of vacuum-arc discharge for different cathode materials are determined. It was shown that vacuum-arc discharge stability can be reached when the magnetic field strength ranges from 40 to 70 G on the cathode surface.

Isotope effect in enthalpy of solvation of the lithium ion

International Nuclear Information System (INIS)

Krestov, G.A.; Egorov, G.I.; Korolev, V.P.

1989-01-01

At 298.15 K, the authors determined the standard enthalpies of solution for 6 LiCl and 7 LiCl in water, heavy water, dimethylsulfoxide (DMSO) and aqueous solutions of DMSO. The authors have established that solvation of 6 Li + is differentiated in water and DMSO to a greater degree than for 7 Li +

Plasma immersion surface modification with metal ion plasma

International Nuclear Information System (INIS)

Brown, I.G.; Yu, K.M.; Godechot, X.

1991-04-01

We describe here a novel technique for surface modification in which metal plasma is employed and by which various blends of plasma deposition and ion implantation can be obtained. The new technique is a variation of the plasma immersion technique described by Conrad and co-workers. When a substrate is immersed in a metal plasma, the plasma that condenses on the substrate remains there as a film, and when the substrate is then implanted, qualitatively different processes can follow, including' conventional' high energy ion implantation, recoil implantation, ion beam mixing, ion beam assisted deposition, and metallic thin film and multilayer fabrication with or without species mixing. Multiple metal plasma guns can be used with different metal ion species, films can be bonded to the substrate through ion beam mixing at the interface, and multilayer structures can be tailored with graded or abrupt interfaces. We have fabricated several different kinds of modified surface layers in this way. 22 refs., 4 figs

Extraction of pertechnetate anion as a ligand in metal complexes with tributylphosphate

International Nuclear Information System (INIS)

Macasek, F.; Kadrabova, J.

1979-01-01

The extraction of the pertechnetate anion has been investigated in the systems tributylphosphate (TBP)-solvent (carbon tetrachloride, n-heptane, chloroform) - metal salt (uranyl nitrate and chloride, thorium nitrate) -ammonium salt. In the absence of a metal, the solvates HTcO 4 xiTBP (i=4) are extracted, while in the presence of uranium and thorium, the distribution of technetium corresponds, to the formation of the mixed complexes: UO 2 (NO 3 )(TcO 4 )x2TBP, UO 2 Cl(TcO 4 )x2TBP and Th(NO 3 ) 3 (TcO 4 )x2TBP. The effective constants of the reactions H + + TcO 4 - + i(TBP)sub(org) reversible (HTcO 4 xiTBP)sub(org), and (MLsub(n)x2TBP)sub(org) + TcO 4 - reversible (MLsub(n-1)TcO 4 x2TBPsub(org) + L were established in the above systems. The extraction of pertechnetate ion is more effective when it is coordinated to a cation solvated by TBP than the extraction in the form of pertechnetate acid solvated by TBP. (author)

Fungitoxicity of metal ions

Energy Technology Data Exchange (ETDEWEB)

Somers, E

1961-01-01

The in vitro fungistatic activity of some twenty-four metal cations has been determine against Alternaria tenuis and Botrytis fabae. The metal salts, mainly nitrates, were tested in aqueous solution without added spore germination stimulant. The logarithm of the metal ion concentration at the ED 50 value has been found to conform to the exponenttial relationship with electronegativity proposed by Danielli and Davies (1951). These results are discussed in relation to the site of action of metal cations on the fungal cell.

Upgraded vacuum arc ion source for metal ion implantation

International Nuclear Information System (INIS)

Nikolaev, A. G.; Oks, E. M.; Savkin, K. P.; Yushkov, G. Yu.; Brown, I. G.

2012-01-01

Vacuum arc ion sources have been made and used by a large number of research groups around the world over the past twenty years. The first generation of vacuum arc ion sources (dubbed ''Mevva,'' for metal vapor vacuum arc) was developed at Lawrence Berkeley National Laboratory in the 1980s. This paper considers the design, performance parameters, and some applications of a new modified version of this kind of source which we have called Mevva-V.Ru. The source produces broad beams of metal ions at an extraction voltage of up to 60 kV and a time-averaged ion beam current in the milliampere range. Here, we describe the Mevva-V.Ru vacuum arc ion source that we have developed at Tomsk and summarize its beam characteristics along with some of the applications to which we have put it. We also describe the source performance using compound cathodes.

Recent Advances in Antimicrobial Hydrogels Containing Metal Ions and Metals/Metal Oxide Nanoparticles

Directory of Open Access Journals (Sweden)

Fazli Wahid

2017-11-01

Full Text Available Recently, the rapid emergence of antibiotic-resistant pathogens has caused a serious health problem. Scientists respond to the threat by developing new antimicrobial materials to prevent or control infections caused by these pathogens. Polymer-based nanocomposite hydrogels are versatile materials as an alternative to conventional antimicrobial agents. Cross-linking of polymeric materials by metal ions or the combination of polymeric hydrogels with nanoparticles (metals and metal oxide is a simple and effective approach for obtaining a multicomponent system with diverse functionalities. Several metals and metal oxides such as silver (Ag, gold (Au, zinc oxide (ZnO, copper oxide (CuO, titanium dioxide (TiO2 and magnesium oxide (MgO have been loaded into hydrogels for antimicrobial applications. The incorporation of metals and metal oxide nanoparticles into hydrogels not only enhances the antimicrobial activity of hydrogels, but also improve their mechanical characteristics. Herein, we summarize recent advances in hydrogels containing metal ions, metals and metal oxide nanoparticles with potential antimicrobial properties.

Yeast enolase: mechanism of activation by metal ions.

Science.gov (United States)

Brewer, J M

1981-01-01

Yeast enolase as prepared by current procedures is inherently chemically homogeneous, though deamidation and partial denaturation can produce electrophoretically distinct forms. A true isozyme of the enzyme exists but does not survive the purification procedure. The chemical sequence for both has been established. The enzyme behaves in solution like a compact, nearly spherical molecule of moderate hydration. Strong intramolecular forces maintain the structure of the individual subunits. The enzyme as isolated is dimeric. If dissociated in the presence of magnesium ions and substrate, then the subunits are active, but if the dissociation occurs in the absence of metal ions, they are inactive until they have reassociated and undergone a first order "annealing" process. Magnesium (II) enhances association. The interaction between the subunits is hydrophobic in character. The enzyme can bind up to 2 mol of most metal ions in "conformational" sites which then allows up to 2 mol of substrate or some substrate analogue to bind. This is not sufficient for catalysis, but conformational metal ions do more than just allow substrate binding. A change in the environment of the metal ions occurs on substrate or substrate analogue binding. There is an absolute correlation between the occurrence of a structural change undergone by the 3-amino analogue of phosphoenolpyruvate and whether the metal ions produce any level of enzymatic activity. For catalysis, two more moles of metal ions, called "catalytic", must bind. There is evidence that the enzymatic reaction involves a carbanion mechanism. It is likely that two more moles of metal ion can bind which inhibit the reaction. The requirement for 2 mol of metal ion per subunit which contribute in different ways to catalysis is exhibited by a number of other enzymes.

Ionic Liquids as Extraction Media for Metal Ions

Science.gov (United States)

Hirayama, Naoki

In solvent extraction separation of metal ions, recently, many researchers have investigated possible use of hydrophobic ionic liquids as extraction media instead of organic solvents. Ionic liquids are salts of liquid state around room temperature and can act not only as solvents but also as ion-exchangers. Therefore, the extraction mechanism of metal ions into ionic liquids is complicated. This review presents current overview and perspective on evaluation of nature of hydrophobic ionic liquids as extraction media for metal ions.

Oxidation of cyclohexane catalyzed by metal-ion-exchanged zeolites.

Science.gov (United States)

Sökmen, Ilkay; Sevin, Fatma

2003-08-01

The ion-exchange rates and capacities of the zeolite NaY for the Cu(II), Co(II), and Pb(II) metal ions were investigated. Ion-exchange equilibria were achieved in approximately 72 h for all the metal ions. The maximum ion exchange of metal ions into the zeolite was found to be 120 mg Pb(II), 110 mg Cu(II), and 100 mg Co(II) per gram of zeolite NaY. It is observed that the exchange capacity of a zeolite varies with the exchanged metal ion and the amount of metal ions exchanged into zeolite decreases in the sequence Pb(II) > Cu(II) > Co(II). Application of the metal-ion-exchanged zeolites in oxidation of cyclohexane in liquid phase with visible light was examined and it is observed that the order of reactivity of the zeolites for the conversion of cyclohexane to cyclohexanone and cyclohexanol is CuY > CoY > PbY. It is found that conversion increases by increase of the empty active sites of a zeolite and the formation of cyclohexanol is favored initially, but the cyclohexanol is subsequently converted to cyclohexanone.

Solvation Effect on Complexation of Alkali Metal Cations by a Calix[4]arene Ketone Derivative.

Science.gov (United States)

Požar, Josip; Nikšić-Franjić, Ivana; Cvetnić, Marija; Leko, Katarina; Cindro, Nikola; Pičuljan, Katarina; Borilović, Ivana; Frkanec, Leo; Tomišić, Vladislav

2017-09-14

The medium effect on the complexation of alkali metal cations with a calix[4]arene ketone derivative (L) was systematically examined in methanol, ethanol, N-methylformamide, N,N-dimethylformamide, dimethyl sulfoxide, and acetonitrile. In all solvents the binding of Na + cation by L was rather efficient, whereas the complexation of other alkali metal cations was observed only in methanol and acetonitrile. Complexation reactions were enthalpically controlled, while ligand dissolution was endothermic in all cases. A notable influence of the solvent on NaL + complex stability could be mainly attributed to the differences in complexation entropies. The higher NaL + stability in comparison to complexes with other alkali metal cations in acetonitrile was predominantly due to a more favorable complexation enthalpy. The 1 H NMR investigations revealed a relatively low affinity of the calixarene sodium complex for inclusion of the solvent molecule in the calixarene hydrophobic cavity, with the exception of acetonitrile. Differences in complex stabilities in the explored solvents, apart from N,N-dimethylformamide and acetonitrile, could be mostly explained by taking into account solely the cation and complex solvation. A considerable solvent effect on the complexation equilibria was proven to be due to an interesting interplay between the transfer enthalpies and entropies of the reactants and the complexes formed.

Metal ion interaction with phosphorylated tyrosine analogue monolayers on gold.

Science.gov (United States)

Petoral, Rodrigo M; Björefors, Fredrik; Uvdal, Kajsa

2006-11-23

Phosphorylated tyrosine analogue molecules (pTyr-PT) were assembled onto gold substrates, and the resulting monolayers were used for metal ion interaction studies. The monolayers were characterized by X-ray photoelectron spectroscopy (XPS), infrared reflection-absorption spectroscopy (IRAS), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS), both prior to and after exposure to metal ions. XPS verified the elemental composition of the molecular adsorbate and the presence of metal ions coordinated to the phosphate groups. Both the angle-dependent XPS and IRAS results were consistent with the change in the structural orientation of the pTyr-PT monolayer upon exposure to metal ions. The differential capacitance of the monolayers upon coordination of the metal ions was evaluated using EIS. These metal ions were found to significantly change the capacitance of the pTyr-PT monolayers in contrast to the nonphosphorylated tyrosine analogue (TPT). CV results showed reduced electrochemical blocking capabilities of the phosphorylated analogue monolayer when exposed to metal ions, supporting the change in the structure of the monolayer observed by XPS and IRAS. The largest change in the structure and interfacial capacitance was observed for aluminum ions, compared to calcium, magnesium, and chromium ions. This type of monolayer shows an excellent capability to coordinate metal ions and has a high potential for use as sensing layers in biochip applications to monitor the presence of metal ions.

Ion implantation and ion assisted coatings for wear resistance in metals

International Nuclear Information System (INIS)

Dearnaley, G.

1986-01-01

The implantation of electrically accelerated ions of chosen elements into the surface of material provides a method for improving surface properties such as wear resistance. High concentrations of nitrogen implanted into metals create obstacles to dislocation movement, and certain combinations of metallic and non-metallic species will also strengthen the surface. The process is best applied to situations involving mild abrasive wear and operating temperatures that are not too high. Some dramatic increases in life have been reported under such favourable conditions. A more recent development has been the combination of a thin coating with reactive ion bombardment designed to enhance adhesion by ion mixing at the interface and so provide hardness by the formation of finely dispersed nitrides, including cubic boron nitride. These coatings often possess vivid and decorative colours as an added benefit. Developments in the equipment for industrial ion implantation now offer more attractive costs per unit area and a potentially greater throughput of work. A versatile group of related hard vacuum treatments is now emerging, involving the use of intense beams of nitrogen ions for the purpose of tailoring metal surfaces to resist wear. (author)

A biosystem for removal of metal ions from water

Energy Technology Data Exchange (ETDEWEB)

Kilbane, J.J. II.

1990-01-01

The presence of heavy metal ions in ground and surface waters constitutes a potential health risk and is an environmental concern. Moreover, processes for the recovery of valuable metal ions are of interest. Bioaccumulation or biosorption is not only a factor in assessing the environmental risk posed by metal ions; it can also be used as a means of decontamination. A biological system for the removal and recovery of metal ions from contaminated water is reported here. Exopolysaccharide-producing microorganisms, including a methanotrophic culture, are demonstrated to have superior metal binding ability, compared with other microbial cultures. This paper describes a biosorption process in which dried biomass obtained from exopolysaccharide-producing microorganisms is encapsulated in porous plastic beads and is used for metal ion binding and recovery. 22 refs., 13 figs.

Ionic association and solvation in solutions of magnesium and nickel perchlorates in acetonitrile

Science.gov (United States)

Kalugin, O. N.; Agieienko, V. N.; Otroshko, N. A.; Moroz, V. V.

2009-02-01

The paper presents the conductometric data on solutions of Mg(ClO4)2 and Ni(ClO4)2 in acetonitrile over the temperature ranges 5-55°C for Mg(ClO4)2 and 25-75°C for Ni(ClO4)2. The extended Lee-Wheaton equation for unsymmetrical electrolytes was used to determine the limiting equivalent conductivities of the Mg2+, Ni2+, and ClO{4/-} ions and first-step ionic association constants with the formation of [KtClO4]+ ion pairs. Lower ionic association constants for Ni(ClO4)2 compared with Mg(ClO4)2 were a consequence of stronger non-Coulomb repulsion in the formation of [KtClO4]+ ion pairs because of the formation of a firmer solvation shell by the nickel compared with magnesium cation. The structure-dynamic parameter of ionic solvation was estimated. It was found that spatial-time correlations in the nearest environment of ions increased in the series ClO{4/-} > Mg2+ > Ni2+.

Metal ion-dependent DNAzymes and their applications as biosensors.

Science.gov (United States)

Lan, Tian; Lu, Yi

2012-01-01

Long considered to serve solely as the genetic information carrier, DNA has been shown in 1994 to be able to act as DNA catalysts capable of catalyzing a trans-esterification reaction similar to the action of ribozymes and protein enzymes. Although not yet found in nature, numerous DNAzymes have been isolated through in vitro selection for catalyzing many different types of reactions in the presence of different metal ions and thus become a new class of metalloenzymes. What remains unclear is how DNA can carry out catalysis with simpler building blocks and fewer functional groups than ribozymes and protein enzymes and how DNA can bind metal ions specifically to perform these functions. In the past two decades, many biochemical and biophysical studies have been carried out on DNAzymes, especially RNA-cleaving DNAzymes. Important insights have been gained regarding their metal-dependent activity, global folding, metal binding sites, and catalytic mechanisms for these DNAzymes. Because of their high metal ion selectivity, one of the most important practical applications for DNAzymes is metal ion detection, resulting in highly sensitive and selective fluorescent, colorimetric, and electrochemical sensors for a wide range of metal ions such as Pb(2+), UO2 2 +,[Formula: see text] including paramagnetic metal ions such as Cu(2+). This chapter summarizes recent progresses in in vitro selection of metal ion-selective DNAzymes, their biochemical and biophysical studies and sensing applications.

Evidence for Reduced Hydrogen-Bond Cooperativity in Ionic Solvation Shells from Isotope-Dependent Dielectric Relaxation

Science.gov (United States)

Cota, Roberto; Ottosson, Niklas; Bakker, Huib J.; Woutersen, Sander

2018-05-01

We find that the reduction in dielectric response (depolarization) of water caused by solvated ions is different for H2O and D2O . This isotope dependence allows us to reliably determine the kinetic contribution to the depolarization, which is found to be significantly smaller than predicted by existing theory. The discrepancy can be explained from a reduced hydrogen-bond cooperativity in the solvation shell: we obtain quantitative agreement between theory and experiment by reducing the Kirkwood correlation factor of the solvating water from 2.7 (the bulk value) to ˜1.6 for NaCl and ˜1 (corresponding to completely uncorrelated motion of water molecules) for CsCl.

Solvated Positron Chemistry. Competitive Positron Reactions with Halide Ions in Water

DEFF Research Database (Denmark)

Christensen, Palle; Pedersen, Niels Jørgen; Andersen, J. R.

1979-01-01

It is shown by means of the angular correlation technique that the binding of positrons to halides is strongly influenced by solvation effects. For aqueous solutions we find increasing values for the binding energies between the halide and the positron with increasing mass of the halide...

State promotion and neutralization of ions near metal surface

International Nuclear Information System (INIS)

Zinoviev, A.N.

2011-01-01

Research highlights: → Multiply charged ion and the charge induced in the metal form a dipole. → Dipole states are promoted into continuum with decreasing ion-surface distance. → These states cross the states formed from metal atom. → Proposed model explains the dominant population of deep bound states. → Observed spectra of emitted Auger electrons prove this promotion model. -- Abstract: When a multiply charged ion with charge Z approaches the metal surface, a dipole is formed by the multiply charged ion and the charge induced in the metal. The states for such a dipole are promoted into continuum with decreasing ion-surface distance and cross the states formed from metal atom. The model proposed explains the dominant population of deep bound states in collisions considered.

Certain regularities of the radiolytic reduction of lead ions in various systems

International Nuclear Information System (INIS)

Chikvaidze, N.M.; Nanobashvili, H.M.; Gabisonya, L.V.

1983-01-01

The radiolysis of the aqueous solutions of the lead salts, chloride, acetate and nitrate, depending on the nature of the acceptor and various factors was studied. The radical and transient products of the radiolysis-solvated electron, ion radicals of the attendant anions, the univalent lead ion were identified and their yields determined by EPR and optical spectroscopy. The decay kinetics of the reducing particles and the kinetics of the formation of anomalous valent lead(I) with its following transformation to metal were studied. The mechanism of the radiation chemical reduction of lead(II) ions is suggested. (author)

Li+ solvation and kinetics of Li+-BF4-/PF6- ion pairs in ethylene carbonate. A molecular dynamics study with classical rate theories

Science.gov (United States)

Chang, Tsun-Mei; Dang, Liem X.

2017-10-01

Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ethylene carbonate (EC) exchange process between the first and second solvation shells around Li+ and the dissociation kinetics of ion pairs Li+-[BF4] and Li+-[PF6] in this solvent. We calculate the exchange rates using transition state theory and correct them with transmission coefficients computed by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found that the residence times of EC around Li+ ions varied from 60 to 450 ps, depending on the correction method used. We found that the relaxation times changed significantly from Li+-[BF4] to Li+-[PF6] ion pairs in EC. Our results also show that, in addition to affecting the free energy of dissociation in EC, the anion type also significantly influences the dissociation kinetics of ion pairing.

Solvation of actinide salts in water using a polarizable continuum model.

Science.gov (United States)

Kumar, Narendra; Seminario, Jorge M

2015-01-29

In order to determine how actinide atoms are dressed when solvated in water, density functional theory calculations have been carried out to study the equilibrium structure of uranium plutonium and thorium salts (UO2(2+), PuO2(2+), Pu(4+), and Th(4+)) both in vacuum as well as in solution represented by a conductor-like polarizable continuum model. This information is of paramount importance for the development of sensitive nanosensors. Both UO2(2+) and PuO2(2+) ions show coordination number of 4-5 with counterions replacing one or two water molecules from the first coordination shell. On the other hand, Pu(4+), has a coordination number of 8 both when completely solvated and also in the presence of chloride and nitrate ions with counterions replacing water molecules in the first shell. Nitrates were found to bind more strongly to Pu(IV) than chloride anions. In the case of the Th(IV) ion, the coordination number was found to be 9 or 10 in the presence of chlorides. Moreover, the Pu(IV) ion shows greater affinity for chlorides than the Th(IV) ion. Adding dispersion and ZPE corrections to the binding energy does not alter the trends in relative stability of several conformers because of error cancelations. All structures and energetics of these complexes are reported.

Comparative study of metal and non-metal ion implantation in polymers: Optical and electrical properties

International Nuclear Information System (INIS)

Resta, V.; Quarta, G.; Farella, I.; Maruccio, L.; Cola, A.; Calcagnile, L.

2014-01-01

The implantation of 1 MeV metal ( 63 Cu + , 107 Ag + , 197 Au + ) and non-metal ( 4 He + , 12 C + ) ions in a polycarbonate (PC) matrix has been studied in order to evaluate the role of ion species in the modification of optical and electrical properties of the polymer. When the ion fluence is above ∼1 × 10 13 ions cm −2 , the threshold for latent tracks overlapping is overcome and π-bonded carbon clusters grow and aggregate forming a network of conjugated C=C bonds. For fluences around 1 × 10 17 ions cm −2 , the aggregation phenomena induce the formation of amorphous carbon and/or graphite like structures. At the same time, nucleation of metal nanoparticles (NPs) from implanted species can take place when the supersaturation threshold is overcome. The optical absorption of the samples increases in the visible range and the optical band gap redshifts from 3.40 eV up to 0.70 eV mostly due to the carbonization process and the formation of C 0x clusters and cluster aggregates. Specific structures in the extinction spectra are observed when metal ions are selected in contrast to the non-metal ion implanted PC, thus revealing the possible presence of noble metal based NPs interstitial to the C 0x cluster network. The corresponding electrical resistance decreases much more when metal ions are implanted with at least a factor of 2 orders of magnitude difference than the non-metal ions based samples. An absolute value of ∼10 7 Ω/sq has been measured for implantation with metals at doses higher than 5 × 10 16 ions cm −2 , being 10 17 Ω/sq the corresponding sheet resistance for pristine PC

Comparative study of metal and non-metal ion implantation in polymers: Optical and electrical properties

Energy Technology Data Exchange (ETDEWEB)

Resta, V., E-mail: vincenzo.resta@le.infn.it [Department of Engineering for Innovation, University of Salento, Via Monteroni, Lecce I-73100 (Italy); Quarta, G. [Department of Engineering for Innovation, University of Salento, Via Monteroni, Lecce I-73100 (Italy); Farella, I. [Institute for Microelectronics and Microsystems – Unit of Lecce, National Council of Research (IMM/CNR), Lecce I-73100 (Italy); Maruccio, L. [Department of Engineering for Innovation, University of Salento, Via Monteroni, Lecce I-73100 (Italy); Cola, A. [Institute for Microelectronics and Microsystems – Unit of Lecce, National Council of Research (IMM/CNR), Lecce I-73100 (Italy); Calcagnile, L. [Department of Engineering for Innovation, University of Salento, Via Monteroni, Lecce I-73100 (Italy)

2014-07-15

The implantation of 1 MeV metal ({sup 63}Cu{sup +}, {sup 107}Ag{sup +}, {sup 197}Au{sup +}) and non-metal ({sup 4}He{sup +}, {sup 12}C{sup +}) ions in a polycarbonate (PC) matrix has been studied in order to evaluate the role of ion species in the modification of optical and electrical properties of the polymer. When the ion fluence is above ∼1 × 10{sup 13} ions cm{sup −2}, the threshold for latent tracks overlapping is overcome and π-bonded carbon clusters grow and aggregate forming a network of conjugated C=C bonds. For fluences around 1 × 10{sup 17} ions cm{sup −2}, the aggregation phenomena induce the formation of amorphous carbon and/or graphite like structures. At the same time, nucleation of metal nanoparticles (NPs) from implanted species can take place when the supersaturation threshold is overcome. The optical absorption of the samples increases in the visible range and the optical band gap redshifts from 3.40 eV up to 0.70 eV mostly due to the carbonization process and the formation of C{sub 0x} clusters and cluster aggregates. Specific structures in the extinction spectra are observed when metal ions are selected in contrast to the non-metal ion implanted PC, thus revealing the possible presence of noble metal based NPs interstitial to the C{sub 0x} cluster network. The corresponding electrical resistance decreases much more when metal ions are implanted with at least a factor of 2 orders of magnitude difference than the non-metal ions based samples. An absolute value of ∼10{sup 7} Ω/sq has been measured for implantation with metals at doses higher than 5 × 10{sup 16} ions cm{sup −2}, being 10{sup 17} Ω/sq the corresponding sheet resistance for pristine PC.

Solution chemistry and separation of metal ions in leached solution

International Nuclear Information System (INIS)

Shibata, J.

1991-01-01

The method to presume a dissolved state of metal ions in an aqueous solution and the technology to separate and concentrate metal ions in a leached solution are described in this paper. It is very important for the separation of metal ions to know the dissolved state of metal ions. If we know the composition of an aqueous solution and the stability constants of metal-ligand complexes, we can calculate and estimate the concentration of each species in the solution. Then, we can decide the policy to separate and concentrate metal ions. There are several methods for separation and purification; hydroxide precipitation method, sulfide precipitation method, solvent extraction method and ion exchange resin method. Solvent extraction has been used in purification processes of copper refinery, uranium refinery, platinum metal refinery and rare earth metal refinery. Fundamental process of solvent extraction, a kind of commercial extractants, a way of determining a suitable extractant and an equipment are discussed. Finally, it will be emphasized how the separation of rare earths is improved in solvent extraction. (author) 21 figs., 8 tabs., 8 refs

Development of a four-zone carousel process packed with metal ion-imprinted polymer for continuous separation of copper ions from manganese ions, cobalt ions, and the constituent metal ions of the buffer solution used as eluent.

Science.gov (United States)

Jo, Se-Hee; Park, Chanhun; Yi, Sung Chul; Kim, Dukjoon; Mun, Sungyong

2011-08-19

A three-zone carousel process, in which Cu(II)-imprinted polymer (Cu-MIP) and a buffer solution were employed as adsorbent and eluent respectively, has been developed previously for continuous separation of Cu²⁺ (product) from Mn²⁺ and Co²⁺ (impurities). Although this process was reported to be successful in the aforementioned separation task, the way of using a buffer solution as eluent made it inevitable that the product stream included the buffer-related metal ions (i.e., the constituent metal ions of the buffer solution) as well as copper ions. For a more perfect recovery of copper ions, it would be necessary to improve the previous carousel process such that it can remove the buffer-related metal ions from copper ions while maintaining the previous function of separating copper ions from the other 2 impure heavy-metal ions. This improvement was made in this study by proposing a four-zone carousel process based on the following strategy: (1) the addition of one more zone for performing the two-step re-equilibration tasks and (2) the use of water as the eluent of the washing step in the separation zone. The operating conditions of such a proposed process were determined on the basis of the data from a series of single-column experiments. Under the determined operating conditions, 3 runs of carousel experiments were carried out. The results of these experiments revealed that the feed-loading time was a key parameter affecting the performance of the proposed process. Consequently, the continuous separation of copper ions from both the impure heavy-metal ions and the buffer-related metal ions could be achieved with a purity of 91.9% and a yield of 92.8% by using the proposed carousel process based on a properly chosen feed-loading time. Copyright © 2011 Elsevier B.V. All rights reserved.

Rechargeable dual-metal-ion batteries for advanced energy storage.

Science.gov (United States)

Yao, Hu-Rong; You, Ya; Yin, Ya-Xia; Wan, Li-Jun; Guo, Yu-Guo

2016-04-14

Energy storage devices are more important today than any time before in human history due to the increasing demand for clean and sustainable energy. Rechargeable batteries are emerging as the most efficient energy storage technology for a wide range of portable devices, grids and electronic vehicles. Future generations of batteries are required to have high gravimetric and volumetric energy, high power density, low price, long cycle life, high safety and low self-discharge properties. However, it is quite challenging to achieve the above properties simultaneously in state-of-the-art single metal ion batteries (e.g. Li-ion batteries, Na-ion batteries and Mg-ion batteries). In this contribution, hybrid-ion batteries in which various metal ions simultaneously engage to store energy are shown to provide a new perspective towards advanced energy storage: by connecting the respective advantages of different metal ion batteries they have recently attracted widespread attention due to their novel performances. The properties of hybrid-ion batteries are not simply the superposition of the performances of single ion batteries. To enable a distinct description, we only focus on dual-metal-ion batteries in this article, for which the design and the benefits are briefly discussed. We enumerate some new results about dual-metal-ion batteries and demonstrate the mechanism for improving performance based on knowledge from the literature and experiments. Although the search for hybrid-ion batteries is still at an early age, we believe that this strategy would be an excellent choice for breaking the inherent disadvantages of single ion batteries in the near future.

Photoemission spectra and density functional theory calculations of 3d transition metal-aqua complexes (Ti-Cu) in aqueous solution.

Science.gov (United States)

Yepes, Diana; Seidel, Robert; Winter, Bernd; Blumberger, Jochen; Jaque, Pablo

2014-06-19

Photoelectron spectroscopy measurements and density functional calculations are combined to determine the lowest electron binding energies of first-row transition-metal aqua ions, titanium through copper, with 3d(1) through 3d(9) electronic configurations, in their most common oxidation states. Vertical ionization energies are found to oscillate considerably between 6.76 and 9.65 eV for the dications and between 7.05 and 10.28 eV for the respective trivalent cations. The metal cations are modeled as [M(H2O)n](q+) clusters (q = 2, 3, and 4; n = 6 and 18) surrounded by continuum solvent. The performance of 10 exchange-correlation functionals, two GGAs, three MGGAs, two HGGAs and three HMGGAs, combined with the MDF10(ECP)/6-31+G(d,p) basis set is assessed for 11 M-O bond distances, 10 vertical ionization energies, 6 adiabatic ionization energies, and the associated reorganization free energies. We find that for divalent cations the HGGA and HMGGA functionals in combination with the 18 water model show the best agreement with experimental vertical ionization energies and geometries; for trivalent ions, the MGGA functionals perform best. The corresponding reorganization free energies (λo) of the oxidized ions are significantly underestimated with all DFT functionals and cluster models. This indicates that the structural reorganization of the solvation shell upon ionization is not adequately accounted for by the simple solvation models used, emphasizing the importance of extended sampling of thermally accessible solvation structures for an accurate computation of this quantity. The photoelectron spectroscopy measurements reported herein provide a comprehensive set of transition-metal redox energetic quantities for future electronic structure benchmarks.

Breast milk metal ion levels in a young and active patient with a metal-on-metal hip prosthesis.

Science.gov (United States)

Nelis, Raymond; de Waal Malefijt, Jan; Gosens, Taco

2013-01-01

Metal-on-metal resurfacing arthroplasty of the hip has been used increasingly over the last 10 years in younger active patients. The dissolution of the metal wear particles results in measurable increases in cobalt and chromium ions in the serum and urine of patients with a metal-on-metal bearing. We measured the cobalt, chromium, and molybdenum ion levels in urine; serum; and breast milk in a young and active patient with a metal-on-metal hip prosthesis after a pathologic fracture of the femoral neck. Metal-on-metal hip prosthesis leads to increasing levels of molybdenum in breast milk in the short-term follow-up. There are no increasing levels of chromium and cobalt ions in breast milk. Besides the already known elevated concentrations in serum of chromium and cobalt after implantation of a metal-on-metal hip prosthesis, we found no increasing levels of chromium and cobalt in urine. Copyright © 2013 Elsevier Inc. All rights reserved.

Extracting metal ions with diphosphonic acid, or derivative thereof

Science.gov (United States)

Horwitz, Earl P.; Gatrone, Ralph C.; Nash, Kenneth L.

1994-01-01

Thermodynamically-unstable complexing agents which are diphosphonic acids and diphosphonic acid derivatives (or sulphur containing analogs), like carboxyhydroxymethanediphosphonic acid and vinylidene-1,1-diphosphonic acid, are capable of complexing with metal ions, and especially metal ions in the II, III, IV, V and VI oxidation states, to form stable, water-soluble metal ion complexes in moderately alkaline to highly-acidic media. However, the complexing agents can be decomposed, under mild conditions, into non-organic compounds which, for many purposes are environmentally-nondamaging compounds thereby degrading the complex and releasing the metal ion for disposal or recovery. Uses for such complexing agents as well as methods for their manufacture are also described.

[Experimental and computation studies of polar solvation

International Nuclear Information System (INIS)

1990-01-01

This report from the Pennsylvania State University contains seven sections: (1) radiative rate effects in solvatlvatochromic probes; (2) intramolecular charge transfer reactions; (3) Solvation dynamics in low temperature alcohols; (4) Ionic solvation dynamics; (5) solvation and proton-transfer dynamics in 7-azaindole; (6) computer simulations of solvation dynamics; (7) solvation in supercritical fluids. 20 refs., 11 figs

The role of solvation in the binding selectivity of the L-type calcium channel.

Science.gov (United States)

Boda, Dezső; Henderson, Douglas; Gillespie, Dirk

2013-08-07

We present grand canonical Monte Carlo simulation results for a reduced model of the L-type calcium channel. While charged residues of the protein amino acids in the selectivity filter are treated explicitly, most of the degrees of freedom (including the rest of the protein and the solvent) are represented by their dielectric response, i.e., dielectric continua. The new aspect of this paper is that the dielectric coefficient in the channel is different from that in the baths. The ions entering the channel, thus, cross a dielectric boundary at the entrance of the channel. Simulating this case has been made possible by our recent methodological development [D. Boda, D. Henderson, B. Eisenberg, and D. Gillespie, J. Chem. Phys. 135, 064105 (2011)]. Our main focus is on the effect of solvation energy (represented by the Born energy) on monovalent vs. divalent ion selectivity in the channel. We find no significant change in selectivity by changing the dielectric coefficient in the channel because the larger solvation penalty is counterbalanced by the enhanced Coulomb attraction inside the channel as soon as we use the Born radii (fitted to experimental hydration energies) to compute the solvation penalty from the Born equation.

Electrical properties of polymer modified by metal ion implantation

International Nuclear Information System (INIS)

Wu Yuguang; Zhang Tonghe; Zhang Huixing; Zhang Xiaoji; Deng Zhiwei; Zhou Gu

2000-01-01

Polyethylene terephthalate (PET) has been modified by Ag, Cr, Cu and Si ion implantation with a dose range from 1x10 16 to 2x10 17 ions cm -2 using a metal vapor vacuum arc (MEVVA) source. The electrical properties of PET have been changed after metal ion implantation. The resistivity of implanted PET decreased obviously with an increase of ion dose. When metal ion dose of 2x10 17 cm -2 was selected, the resistivity of PET could be less than 10 Ω cm, but when Si ions are implanted, the resistivity of PET would be up to several hundred Ω cm. The results show that the conductive behavior of a metal ion implanted sample is obviously different from Si implantation one. The changes of the structure and composition have been observed with transmission electron microscope (TEM) and X-ray diffraction (XRD). The surface structure is varying after ion implantation and it is believed that the change would cause the improvement of the conductive properties. The mechanism of electrical conduction will be discussed

Extracting metal ions with diphosphonic acid, or derivative thereof

Science.gov (United States)

Horwitz, E.P.; Gatrone, R.C.; Nash, K.L.

1994-07-26

Thermodynamically-unstable complexing agents which are diphosphonic acids and diphosphonic acid derivatives (or sulfur containing analogs), like carboxyhydroxymethanediphosphonic acid and vinylidene-1,1-diphosphonic acid, are capable of complexing with metal ions, and especially metal ions in the II, III, IV, V and VI oxidation states, to form stable, water-soluble metal ion complexes in moderately alkaline to highly-acidic media. However, the complexing agents can be decomposed, under mild conditions, into non-organic compounds which, for many purposes are environmentally-nondamaging compounds thereby degrading the complex and releasing the metal ion for disposal or recovery. Uses for such complexing agents as well as methods for their manufacture are also described. 1 fig.

Effective charge of energetic ions in metals

International Nuclear Information System (INIS)

Kitagawa, M.; Brandt, W.

1983-01-01

The effective charge of energetic ion, as derived from stopping power of metals, is calculated by use of a dielectronic-response function method. The electronic distribution in the ion is described through the variational principle in a statistical approximation. The dependences of effective charge on the ion velocity, atomic number and r/sub s/-value of metal are derived at the low-velocity region. The effective charge becomes larger than the real charge of ion due to the close collisions. We obtain the quasi-universal equation of the fractional effective electron number of ion as a function of the ratio between the ionic size and the minimum distance approach. The comparsion between theoretical and experimental results of the effective charge is performed for the cases of N ion into Au, C and Al. We also discuss the equipartition rule of partially ionized ion at the high-velocity region

Electrolyte Suitable for Use in a Lithium Ion Cell or Battery

Science.gov (United States)

McDonald, Robert C. (Inventor)

2014-01-01

Electrolyte suitable for use in a lithium ion cell or battery. According to one embodiment, the electrolyte includes a fluorinated lithium ion salt and a solvent system that solvates lithium ions and that yields a high dielectric constant, a low viscosity and a high flashpoint. In one embodiment, the solvent system includes a mixture of an aprotic lithium ion solvating solvent and an aprotic fluorinated solvent.

A molecular dynamics study for the isomerization of Ar solvated (benzene){sub 2}-K{sup +} heteroclusters

Energy Technology Data Exchange (ETDEWEB)

Alberti, M. [CERQT, Departament de Quimica Fisica Parc Cientific, Universitat de Barcelona, Marti i Franques, 1, 08028 Barcelona (Spain); Pacifici, L. [Department of Mathematics and Computer Science, University of Perugia, via Vanvitelli, 1 06123 Perugia (Italy); Lagana, A. [Department of Chemistry, University of Perugia, via Elce di Sotto, 8 06123 Perugia (Italy)], E-mail: lag@dyn.unipg.it; Aguilar, A. [CERQT, Departament de Quimica Fisica Parc Cientific, Universitat de Barcelona, Marti i Franques, 1, 08028 Barcelona (Spain)

2006-08-21

A dynamical study of the (benzene){sub 2}-K{sup +} heteroclusters solvated by Ar atoms has been performed using an analytical force field of the atom (ion)-bond type. An analysis of the relevant calculated structural and energetic properties of these systems is made to understand involved molecular processes. The key effect found in the calculations is the tieing up of the two rings to sandwich K{sup +} and the weaking of this effect by solvation.

New Proton-Ionizable, Calixarene-Based Ligands for Selective Metal Ion Separations

Energy Technology Data Exchange (ETDEWEB)

Bartsch, Richard A.

2012-06-04

The project objective was the discovery of new ligands for performing metal ion separations. The research effort entailed the preparation of new metal ion complexing agents and polymers and their evaluation in metal ion separation processes of solvent extraction, synthetic liquid membrane transport, and sorption. Structural variations in acyclic, cyclic, and bicyclic organic ligands were used to probe their influence upon the efficiency and selectivity with which metal ion separations can be performed. A unifying feature of the ligand structures is the presence of one (or more) side arm with a pendent acidic function. When a metal ion is complexed within the central cavity of the ligand, ionization of the side arm(s) produces the requisite anion(s) for formation of an overall electroneutral complex. This markedly enhances extraction/transport efficiency for separations in which movement of aqueous phase anions of chloride, nitrate, or sulfate into an organic medium would be required. Through systematic structural variations, new ligands have been developed for efficient and selective separations of monovalent metal ions (e.g., alkali metal, silver, and thallium cations) and of divalent metal ion species (e.g., alkaline earth metal, lead, and mercury cations). Research results obtained in these fundamental investigations provide important insight for the design and development of ligands suitable for practical metal ion separation applications.

Designer ligands: The search for metal ion selectivity

Directory of Open Access Journals (Sweden)

Perry T. Kaye

2011-03-01

Full Text Available The paper reviews research conducted at Rhodes University towards the development of metal-selective ligands. The research has focused on the rational design, synthesis and evaluation of novel ligands for use in the formation of copper complexes as biomimetic models of the metalloenzyme, tyrosinase, and for the selective extraction of silver, nickel and platinum group metal ions in the presence of contaminating metal ions. Attention has also been given to the development of efficient, metal-selective molecular imprinted polymers.

Solvation in supercritical water

International Nuclear Information System (INIS)

Cochran, H.D.; Cummings, P.T.; Karaborni, S.

1991-01-01

The aim of this work is to determine the solvation structure in supercritical water composed with that in ambient water and in simple supercritical solvents. Molecular dynamics studies have been undertaken of systems that model ionic sodium and chloride, atomic argon, and molecular methanol in supercritical aqueous solutions using the simple point charge model of Berendsen for water. Because of the strong interactions between water and ions, ionic solutes are strongly attractive in supercritical water, forming large clusters of water molecules around each ion. Methanol is found to be a weakly-attractive solute in supercritical water. The cluster of excess water molecules surrounding a dissolved ion or polar molecule in supercritical aqueous solutions is comparable to the solvent clusters surrounding attractive solutes in simple supercritical fluids. Likewise, the deficit of water molecules surrounding a dissolved argon atom in supercritical aqueous solutions is comparable to that surrounding repulsive solutes in simple supercritical fluids. The number of hydrogen bonds per water molecule in supercritical water was found to be about one third the number in ambient water. The number of hydrogen bonds per water molecule surrounding a central particle in supercritical water was only mildly affected by the identify of the central particle--atom, molecule, or ion. These results should be helpful in developing a qualitative understanding of important processes that occur in supercritical water. 29 refs., 6 figs

Ion microprobe analysis of metallic pigments

International Nuclear Information System (INIS)

Pelicon, P.; Simcic, J.; Budnar, M.; Klanjsek-Gunde, M.; Kunavaer, M.

2001-01-01

Full text: Metallic paints consist of metallic flakes dispersed m a resinous binder, i.e. a light-element polymer matrix. The spatial distribution and orientation of metallic flakes inside the matrix determines the covering efficiency of the paint, glossiness, and its angular-dependent properties such as lightness flop or color flop (two-tone). Such coatings are extensively used for a functional (i.e. security) as well as decorative purpose. The ion microbeam analysis of two types of silver paint with imbedded metallic flake has been performed to test the ability of the ion microbeam spectroscopic methods on this type of samples. The average sizes of the aluminium flakes were 23 (size distribution 10-37) and 49 (size distribution 34-75) micrometers, respectively. The proton beam with the size of 2x2 micrometers at Ljubljana ion microprobe has been used to scan the surface of the pigments. PIXE mapping of Al Kα map shows lateral distribution of the aluminum flakes, whereas the RBS slicing method reveals tomographic image of the flakes in uppermost 5 micrometers of the pigment layer. The flake distribution in the larger layer depths has been accessed by RBS analysis in a point mode. (author)

Chromium and cobalt ion concentrations in blood and serum following various types of metal-on-metal hip arthroplasties

DEFF Research Database (Denmark)

Jantzen, Christopher; Jørgensen, Henrik L; Duus, Benn R

2013-01-01

Widely different metal ion concentrations in blood and serum have been reported with metal-on-metal (MoM) implants. We reviewed the literature on blood and serum ion concentrations of chromium (Cr) and cobalt (Co) following various MoM hip arthroplasties.......Widely different metal ion concentrations in blood and serum have been reported with metal-on-metal (MoM) implants. We reviewed the literature on blood and serum ion concentrations of chromium (Cr) and cobalt (Co) following various MoM hip arthroplasties....

Validation of ion chromatography for the determination of transition metal ions along with alkali, alkaline earth metal elements for uranium oxide fuel

International Nuclear Information System (INIS)

Kelkar, Anoop; Prakash, Amrit; Afzal, Mohd.; Panakkal, J.P.

2009-02-01

The present report describes the use of Ion chromatography (IC) methods with spectrophotometric and direct conductivity detection for the determination of transition metal elements and alkali alkaline earth metal ions in UO 2 pellets. Transmet analytical column and Metrosep- cation 1-2 column were used for the separation of transition metal elements and alkali and alkaline earth metal elements respectively. Oxalic acid and mixture of pyridine 2,6-dicarboxylic acid (PDCA), Na 2 SO 4 and NaCl were used as mobile phase for the separation of transition metal ions and monitored after post - column reaction with 4,2-pyridylazo resorcinol (PAR) at 520nm spectrophotometrically. In the determination of alkali and alkaline earth metal ions the interference of transition metals are removed by complexing them with PDCA. Mixture of tartaric acid and PDCA employed in the separation of alkali and alkaline earth metal ions and monitored on direct conductivity detector. Mobile phase composition was optimised for the base line separation. Calibration plots of Fe 3+ , Cu 2+ , Ni 2+ , Co 2+ , Cd 2+ , Mn 2+ , Li + , Na + , K + , Mg 2+ , Ca 2+ and Sr 2+ were linear over a wide dynamic range with regression coefficient better than 0.999. Detection limit of above ions were between 5-30ppb. To prevent the overloading of the cation exchange column, uranium matrix was removed from UO 2 sample by solvent extraction with 30% TBP - TOPO/CCl 4 . Ten sintered UO2 pellets of same lot were analysed and R.S.D. ±10% was obtained. These methods were validated by analysis of ILCE standards of UO 2 . (author)

Benzonitrile: Electron affinity, excited states, and anion solvation

Science.gov (United States)

Dixon, Andrew R.; Khuseynov, Dmitry; Sanov, Andrei

2015-10-01

We report a negative-ion photoelectron imaging study of benzonitrile and several of its hydrated, oxygenated, and homo-molecularly solvated cluster anions. The photodetachment from the unsolvated benzonitrile anion to the X ˜ 1 A 1 state of the neutral peaks at 58 ± 5 meV. This value is assigned as the vertical detachment energy (VDE) of the valence anion and the upper bound of adiabatic electron affinity (EA) of benzonitrile. The EA of the lowest excited electronic state of benzonitrile, a ˜ 3 A 1 , is determined as 3.41 ± 0.01 eV, corresponding to a 3.35 eV lower bound for the singlet-triplet splitting. The next excited state, the open-shell singlet A ˜ 1 A 1 , is found about an electron-volt above the triplet, with a VDE of 4.45 ± 0.01 eV. These results are in good agreement with ab initio calculations for neutral benzonitrile and its valence anion but do not preclude the existence of a dipole-bound state of similar energy and geometry. The step-wise and cumulative solvation energies of benzonitrile anions by several types of species were determined, including homo-molecular solvation by benzonitrile, hydration by 1-3 waters, oxygenation by 1-3 oxygen molecules, and mixed solvation by various combinations of O2, H2O, and benzonitrile. The plausible structures of the dimer anion of benzonitrile were examined using density functional theory and compared to the experimental observations. It is predicted that the dimer anion favors a stacked geometry capitalizing on the π-π interactions between the two partially charged benzonitrile moieties.

Metal ion separations with proton-ionizable Lariat Ethers and their polymers

International Nuclear Information System (INIS)

Bartsch, R.A.

1993-01-01

The preparation of novel and specific organic complexing agents may lead to the development of new separation systems for aqueous metal ions. Thus the introduction of highly lipophilic oximes led to the current utilization of these compounds as commercial extractants for the hydrometallurgy of nonferrous metals. Crown ethers (macrocyclic polyethers) have been employed in the laboratory-scale solvent extraction of alkali-metal, alkaline-earth, and other metal cations into organic phases. Attachment of side arms to crown ethers gives lariat ethers. The presence of one or more potential coordination sites in the side arm of the lariat ether may produce substantial changes in the selectivity and efficiency of metal ion complexation. It has been demonstrated that concomitant transfer of an aqueous phase anion into the organic medium is not required for metal ion extraction. This factor is of immense importance to potential practical applications of these proton-ionizable crown ethers in which the common, hard, aqueous phase anions would be involved. Another advantage of proton-ionizable lariat ethers is the ease with which extracted metal ions may be stripped from the organic phase by shaking with aqueous mineral acid. Thus both metal ion extraction and stripping are facilitated by pendent proton-ionizable groups. Most of the hazardous metal ion species in the Hanford Site tank wastes are members of the alkali-metal, alkaline-earth, lanthanide, and actinide families. These hard metal ion species prefer association with hard donor atoms, such as oxygens. Therefore, crown and lariat ethers are well-suited for complexation with such metal ion species

Negative ion photoelectron spectroscopy of solvated electron cluster anions, (H2O)n- and (NH3)n-

International Nuclear Information System (INIS)

Lee, G.H.; Arnold, S.T.; Eaton, J.G; Sarkas, H.W.; Bowen, K.H.; Ludewigt, C.; Haberland, H.

1991-01-01

The photodetachment spectra of (H 2 O) - n=2-69 and (NH 3 ) - n=41-1100 have been recorded, and vertical detachment energies (VDEs) were obtained from the spectra. For both systems, the cluster anion VDEs increase smoothly with increasing sizes and most species plot linearly with n -1/3 , extrapolating to a VDE (n = ∞) value which is very close to the photoelectric threshold energy for the corresponding condensed phase solvated electron system. The linear extrapolation of this data to the analogous condensed phase property suggests that these cluster anions are gas phase counterparts to solvated electrons, i.e. they are embryonic forms of hydrated and ammoniated electrons which mature with increasing cluster size toward condensed phase solvated electrons. (orig.)

Negative ion photoelectron spectroscopy of solvated electron cluster anions, (H2O){/n -} and (NH3){/n -}

Science.gov (United States)

Lee, G. H.; Arnold, S. T.; Eaton, J. G.; Sarkas, H. W.; Bowen, K. H.; Ludewigt, C.; Haberland, H.

1991-03-01

The photodetachment spectra of (H2O){/n =2-69/-} and (NH3){/n =41-1100/-} have been recorded, and vertical detachment energies (VDEs) were obtained from the spectra. For both systems, the cluster anion VDEs increase smoothly with increasing sizes and most species plot linearly with n -1/3, extrapolating to a VDE ( n=∞) value which is very close to the photoelectric threshold energy for the corresponding condensed phase solvated electron system. The linear extrapolation of this data to the analogous condensed phase property suggests that these cluster anions are gas phase counterparts to solvated electrons, i.e. they are embryonic forms of hydrated and ammoniated electrons which mature with increasing cluster size toward condensed phase solvated electrons.

A new biotechnology for recovering heavy metal ions from wastewater

International Nuclear Information System (INIS)

Darnall, D.W.; Gabel, A.

1989-01-01

This paper reports that bio-recovery systems has developed a new sorption process for removing toxic metal ions from water. This process is based upon the natural, very strong affinity for biological materials, such as the cell walls of plants and microorganisms, for heavy metal ions such as uranium, cadmium, cobalt, nickel, etc.. Biological materials, primarily algae, have been immobilized in a polymer to produce a biological ion exchange resin, AlgaSORB. The material has a remarkable affinity for heavy metal ions and is capable of concentrating these ions by a factor of may thousand-fold. Additionally, the bound metals can be stripped and recovered from the algal material in a manner similar to conventional resins

Indolenine meso-substituted dibenzotetraaza[14]annulene and its coordination chemistry toward the transition metal ions Mn(III), Fe(III), Co(II), Ni(II), Cu(II), and Pd(II).

Science.gov (United States)

Khaledi, Hamid; Olmstead, Marilyn M; Ali, Hapipah Mohd; Thomas, Noel F

2013-02-18

A new dibenzotetraaza[14]annulene bearing two 3,3-dimethylindolenine fragments at the meso positions (LH(2)), has been synthesized through a nontemplate method. X-ray crystallography shows that the whole molecule is planar. The basicity of the indolenine ring permits the macrocycle to be protonated external to the core and form LH(4)(2+)·2Cl(-). Yet another structural modification having strong C-H···π interactions was found in the chloroform solvate of LH(2). The latter two modifications are accompanied by a degree of nonplanar distortion. The antiaromatic core of the macrocycle can accommodate a number of metal ions, Mn(III), Fe(III), Co(II), Ni(II) and Cu(II), to form complexes of [Mn(L)Br], [Mn(L)Cl], [Fe(LH(2))Cl(2)](+)·Cl(-), [Co(L)], [Ni(L)], and [Cu(L)]. In addition, the reaction of LH(2) with the larger Pd(II) ion leads to the formation of [Pd(2)(LH(2))(2)(OAc)(4)] wherein the macrocycle acts as a semiflexible ditopic ligand to coordinate pairs of metal ions via its indolenine N atoms into dinuclear metallocycles. The compounds LH(2), [Co(L)], and [Ni(L)] are isostructural and feature close π-stacking as well as linear chain arrangements in the case of the metal complexes. Variable temperature magnetic susceptibility measurements showed thermally induced paramagnetism in [Ni(L)].

Metal ion sequestration: An exciting dimension for molecularly ...

African Journals Online (AJOL)

The use of a tight binding macrocyclic ligand to complex a metal ion so that this serves as receptee on the Molecularly Imprinted Polymer (MIP) receptor as described here affords a sequestration route for a targeted metal ion, with potential for environmental remediation and restoration applications. Ethylene glycol ...

Gibbs energies of protonation and complexation of platinum and vanadate metal ions with naringenin and phenolic acids: Theoretical calculations associated with experimental values

International Nuclear Information System (INIS)

Fazary, Ahmed E.; Alshihri, Ayed S.; Alfaifi, Mohammad Y.; Saleh, Kamel A.; Elbehairi, Serag Eldin I.; Fawy, Khaled F.; Abd-Rabboh, Hisham S.M.

2016-01-01

Highlights: • The experimental thermodynamic equilibrium and stability constants of vanadium and platinum complexes involving naringin, ferulic acid, p-coumaric acid, caffeic acid, vanillic acid, sinapic acid, and gallic acid were determined. • The theoretical calculations of the free energy changes associated with the ligand protonation, and metal ion–ligand complex formation equilibria using density function theory calculations, providing a complete picture of the microscopic equilibria of the studied complex systems. - Abstract: The Experimental thermodynamic equilibrium (pK_a values) and stability (log β) constants of vanadium and platinum binary and mixed ligand complexes involving naringenin, ferulic acid, p-coumaric acid, caffeic acid, vanillic acid, sinapic acid, and gallic acid were determined at 310.15 K in 0.16 mol·dm"−"3 KCl aqueous solutions using pH-potentiometric technique and by means of two estimation models (HYPERQUAD 2008 and Bjerrum–Calvin). The theoretical calculations of overall protonation and stability constants of the metal complex species in solution were predicted as the free energy change associated with the ligand protonation, and metal ion–ligand complex formation equilibria (species solvation/de-solvation) using ab initio and density function theory (DFT) calculations. The usage of the experimental potentiometry technique and theoretical predictions provides a complete picture of the microscopic equilibria of the studied systems (vanadium/platinum–naringenin–phenolic acid). Specifically, this theoretically DFT predications would be useful to determine the most real protonation constants of the studied bioligands in which the binding sites changes due to the ligand protonation/deprotonation equilibria. Also, the complexing capacities of vanadium and platinum towards naringenin, ferulic acid, p-coumaric acid, caffeic acid, vanillic acid, sinapic acid, and gallic acid in solutions were evaluated and discussed. From the

Cation-Size-Dependent Conformational Locking of Glutamic Acid by Alkali Ions: Infrared Photodissociation Spectroscopy of Cryogenic Ions.

Science.gov (United States)

Klyne, Johanna; Bouchet, Aude; Ishiuchi, Shun-Ichi; Fujii, Masaaki; Dopfer, Otto

2018-03-01

Consolidated knowledge of conformation and stability of amino acids and their clusters is required to understand their biochemical recognition. Often, alkali ions interact with amino acids and proteins. Herein, infrared photodissociation (IRPD) spectra of cryogenic metalated glutamic acid ions (GluM + , M = Li-Cs) are systematically analyzed in the isomer-specific fingerprint and XH stretch ranges (1100-1900, 2600-3600 cm -1 ) to provide a direct measure for cation-size-dependent conformational locking. GluM + ions are generated by electrospray ionization and cooled down to 15 K in a cryogenic quadrupole ion trap. The assignment of the IRPD spectra is supported by density functional theory calculations at the dispersion-corrected B3LYP-D3/aug-cc-pVTZ level. In the global minimum of GluM + , the flexibility of Glu is strongly reduced by the formation of rigid ionic CO···M + ···OC metal bridges, corresponding to charge solvation. The M + binding energy decreases monotonically with increasing cation size from D 0 = 314 to 119 kJ/mol for Li-Cs. Whereas for Li and Na only the global minimum of GluM + is observed, for K-Cs at least three isomers exist at cryogenic temperature. The IRPD spectra of cold GluM + ions are compared to IR multiple-photon dissociation spectra measured at room temperature. Furthermore, we elucidate the differences of the impact of protonation and metalation on the structure and conformational locking of Glu.

Complexation ion-exchange chromatography of some metal ions on papers impregnated with Ti(IV)-based inorganic ion exchangers.

Science.gov (United States)

Sharma, S D; Gupta, R

2000-02-01

The chromatographic behavior of 40 metal ions is studied on titanium (IV) arsenate, titanium (IV) phosphate-, titanium (IV) molybdate-, titanium(IV) tungstate-, and titanium(IV) selenite-impregnated papers in 0.1M oxalic, citric, and tartaric acid as mobile phases. Similar studies are carried out on Whatman No. 1 papers for comparison. The ion-exchange capacity of these papers is determined, and their selectivity for different cations is discussed. The mechanism of migration is explained in terms of ion-exchange, precipitation, and adsorption. The prediction of elution sequence from RF values is also checked. The average Ri is found to be almost linearly dependent on the charge of the metal ions. The effect of the pKa of complexing acids on average RF values of 3d series metal ions is explained. A number of binary and ternary separations are achieved.

Adsorption of Heavy Metal Ions from Aqueous Solutions by Bentonite Nanocomposites.

Science.gov (United States)

Ma, Jing; Su, Guojun; Zhang, Xueping; Huang, Wen

2016-08-01

A series of bentonite nanocomposites have been synthesized by modifying bentonite with hexadecyltrimethylammonium bromide (CTMAB) and the common complexing agents, complexone (ethylene diamine tetraacetic acid, EDTA) or mercaptocomplexant (2-Mercaptobenzothiazole, MBT). These adsorbents are used to remove heavy metal ions (Cu(2+), Zn(2+), Mn(2+),Co(2+)). The Bent-CTMAB-MBT adsorbed metal ions are higher than Bent-CTMAB-EDTA under the same ion concentration in AAS. Compared with the single ion system, the adsorption of the mixed ion system of Cu(2+), Zn(2+), Mn(2+), Co(2+) had decreased differently. In the mixed system, the adsorption of Mn(2+) is significantly lower, but the adsorption of Cu(2+) was highest. The adsorption sequence of these four metal ions was Cu(2+) > Zn(2+) > Co(2+) > Mn(2+), and the selective adsorption was closely related to the hydration energy of heavy metal ions. We could remove more metal ions in different stages with the adsorption sequence.

On the relation between Marcus theory and ultrafast spectroscopy of solvation kinetics

Science.gov (United States)

Roy, Santanu; Galib, Mirza; Schenter, Gregory K.; Mundy, Christopher J.

2018-01-01

The phenomena of solvent exchange control the process of solvating ions, protons, and charged molecules. Building upon our extension of Marcus' philosophy of electron transfer, we provide a new perspective of ultrafast solvent exchange mechanism around ions measurable by two-dimensional infrared (2DIR) spectroscopy. In this theory, solvent rearrangement drives an ion-bound water to an activated state of higher coordination number, triggering ion-water separation that leads to the solvent-bound state of the water molecule. This ion-bound to solvent-bound transition rate for a BF4--water system is computed using ab initio molecular dynamics and Marcus theory, and is found to be in excellent agreement with the 2DIR measurement.

Metal ion removal from aqueous solution using physic seed hull.

Science.gov (United States)

Mohammad, Masita; Maitra, Saikat; Ahmad, Naveed; Bustam, Azmi; Sen, T K; Dutta, Binay K

2010-07-15

The potential of physic seed hull (PSH), Jantropha curcas L. as an adsorbent for the removal of Cd(2+) and Zn(2+) metal ions from aqueous solution has been investigated. It has been found that the amount of adsorption for both Cd(2+) and Zn(2+) increased with the increase in initial metal ions concentration, contact time, temperature, adsorbent dosage and the solution pH (in acidic range), but decreased with the increase in the particle size of the adsorbent. The adsorption process for both metal ions on PSH consists of three stages-a rapid initial adsorption followed by a period of slower uptake of metal ions and virtually no uptake at the final stage. The kinetics of metal ions adsorption on PSH followed a pseudo-second-order model. The adsorption equilibrium data were fitted in the three adsorption isotherms-Freundlich, Langmuir and Dubinin-Radushkevich isotherms. The data best fit in the Langmuir isotherm indication monolayer chemisorption of the metal ions. The adsorption capacity of PSH for both Zn(2+) and Cd(2+) was found to be comparable with other available adsorbents. About 36-47% of the adsorbed metal could be leached out of the loaded PSH using 0.1M HCl as the eluting medium. 2010 Elsevier B.V. All rights reserved.

Applications of the solvation parameter model in reversed-phase liquid chromatography.

Science.gov (United States)

Poole, Colin F; Lenca, Nicole

2017-02-24

The solvation parameter model is widely used to provide insight into the retention mechanism in reversed-phase liquid chromatography, for column characterization, and in the development of surrogate chromatographic models for biopartitioning processes. The properties of the separation system are described by five system constants representing all possible intermolecular interactions for neutral molecules. The general model can be extended to include ions and enantiomers by adding new descriptors to encode the specific properties of these compounds. System maps provide a comprehensive overview of the separation system as a function of mobile phase composition and/or temperature for method development. The solvation parameter model has been applied to gradient elution separations but here theory and practice suggest a cautious approach since the interpretation of system and compound properties derived from its use are approximate. A growing application of the solvation parameter model in reversed-phase liquid chromatography is the screening of surrogate chromatographic systems for estimating biopartitioning properties. Throughout the discussion of the above topics success as well as known and likely deficiencies of the solvation parameter model are described with an emphasis on the role of the heterogeneous properties of the interphase region on the interpretation and understanding of the general retention mechanism in reversed-phase liquid chromatography for porous chemically bonded sorbents. Copyright © 2016 Elsevier B.V. All rights reserved.

Bioavailability of Metal Ions and Evolutionary Adaptation

Directory of Open Access Journals (Sweden)

Rolando P. Hong Enriquez

2012-10-01

Full Text Available The evolution of life on earth has been a long process that began nearly 3,5 x 109 years ago. In their initial moments, evolution was mainly influenced by anaerobic environments; with the rise of O2 and the corresponding change in bioavailability of metal ions, new mechanisms of survival were created. Here we review the relationships between ancient atmospheric conditions, metal ion bioavailability and adaptation of metals homeostasis during early evolution. A general picture linking geochemistry, biochemistry and homeostasis is supported by the reviewed literature and is further illustrated in this report using simple database searches.

Means for obtaining a metal ion beam from a heavy-ion cyclotron source

Science.gov (United States)

Hudson, E.D.; Mallory, M.L.

1975-08-01

A description is given of a modification to a cyclotron ion source used in producing a high intensity metal ion beam. A small amount of an inert support gas maintains the usual plasma arc, except that it is necessary for the support gas to have a heavy mass, e.g., xenon or krypton as opposed to neon. A plate, fabricated from the metal (or anything that can be sputtered) to be ionized, is mounted on the back wall of the ion source arc chamber and is bombarded by returning energetic low-charged gas ions that fail to cross the initial accelerating gap between the ion source and the accelerating electrode. Some of the atoms that are dislodged from the plate by the returning gas ions become ionized and are extracted as a useful beam of heavy ions. (auth)

Chromatography Of Metal Ions On Wood Cellulose Impregnated ...

African Journals Online (AJOL)

Adsorption chromatography of some heavy metal ions on wood cellulose of saw dust (wood waste dust) modified with hydrochloric acid, urea and thiourea was studied. Atomic absorption spectrophotometry (AAS) was used to determine the initial concentration of solutions of Zn2+, Cu2+, Ni2+, Pb2+, and Fe3+ metal ions.

Metal hydride compositions and lithium ion batteries

Energy Technology Data Exchange (ETDEWEB)

Young, Kwo; Nei, Jean

2018-04-24

Heterogeneous metal hydride (MH) compositions comprising a main region comprising a first metal hydride and a secondary region comprising one or more additional components selected from the group consisting of second metal hydrides, metals, metal alloys and further metal compounds are suitable as anode materials for lithium ion cells. The first metal hydride is for example MgH.sub.2. Methods for preparing the composition include coating, mechanical grinding, sintering, heat treatment and quenching techniques.

Elucidating the Solvation Structure and Dynamics of Lithium Polysulfides Resulting from Competitive Salt and Solvent Interactions

Energy Technology Data Exchange (ETDEWEB)

Rajput, Nav Nidhi; Murugesan, Vijayakumar; Shin, Yongwoo; Han, Kee Sung; Lau, Kah Chun; Chen, Junzheng; Liu, Jun; Curtiss, Larry A.; Mueller, Karl T.; Persson, Kristin A.

2017-04-10

Fundamental molecular level understanding of functional properties of liquid solutions provides an important basis for designing optimized electrolytes for numerous applica-tions. In particular, exhaustive knowledge of solvation structure, stability and transport properties is critical for developing stable electrolytes for fast charging and high energy density next-generation energy storage systems. Here we report the correlation between solubility, solvation structure and translational dynamics of a lithium salt (Li-TFSI) and polysulfides species using well-benchmarked classical molecular dynamics simulations combined with nuclear magnetic resonance (NMR). It is observed that the polysulfide chain length has a significant effect on the ion-ion and ion-solvent interaction as well as on the diffusion coefficient of the ionic species in solution. In particular, extensive cluster formation is observed in lower order poly-sulfides (Sx2-; x≤4), whereas the longer polysulfides (Sx2-; x>4) show high solubility and slow dynamics in the solu-tion. It is observed that optimal solvent/salt ratio is essen-tial to control the solubility and conductivity as the addi-tion of Li salt increases the solubility but decreases the mo-bility of the ionic species. This work provides a coupled theoretical and experimental study of bulk solvation struc-ture and transport properties of multi-component electro-lyte systems, yielding design metrics for developing optimal electrolytes with improved stability and solubility.

Application of ion implantation in metals and alloys

International Nuclear Information System (INIS)

Dearnaley, G.

1981-01-01

Ion implantation first became established as a precise method of introducing dopant elements into semiconductors. It is now appreciated that there may be equally important applications in metallic tools or components with the purpose of improving their resistance to wear, fatigue or corrosion. Nitrogen ions implanted into steels pin dislocations and thereby harden the metal. Some metallic ions such as yttrium reduce the tendency for oxidative wear. There is a fairly good understanding of how both treatments can provide a long-lasting protection that extends to many times the original depth of implantation. Nitrogen implantation also improves the wear resistance of Co-cemented tungsten carbide and of hard chromium electroplated coatings. These treatments have wide application in press tools, molds, dies and other metal-forming tools as well as in a more limited variety of cutting tools. Some striking improvements can be achieved in the corrosion field, but there are economic and technical reasons for concluding that practical applications of ion implantation will be more restricted and specialized in this area. The most promising area is that in which mechanical stress and oxidation coexist. When a metallic species has to be introduced, a promising new development is to bombard a thin coating of the metal at an elevated temperature. Several powerful mechanisms of radiation-enhanced diffusion can bring about a complete intermixing. Examples of how this has been used to produce wear resistant surfaces in titanium are given. Finally, the equipment developed for the large scale application of the ion implantation process in the engineering field is described

Ion beam analysis of metal ion implanted surfaces

Energy Technology Data Exchange (ETDEWEB)

Evans, P.J.; Chu, J.W.; Johnson, E.P.; Noorman, J.T. [Australian Nuclear Science and Technology Organisation, Lucas Heights, NSW (Australia); Sood, D.K. [Royal Melbourne Inst. of Tech., VIC (Australia)

1993-12-31

Ion implantation is an established method for altering the surface properties of many materials. While a variety of analytical techniques are available for the characterisation of implanted surfaces, those based on particle accelerators such as Rutherford backscattering (RBS) and nuclear reaction analysis (NRA) provide some of the most useful and powerful for this purpose. Application of the latter techniques to metal ion implantation research at ANSTO will be described with particular reference to specific examples from recent studies. Where possible, the information obtained from ion beam analysis will be compared with that derived from other techniques such as Energy Dispersive X-ray (EDX) and Auger spectroscopies. 4 refs., 5 figs.

Ion beam analysis of metal ion implanted surfaces

Energy Technology Data Exchange (ETDEWEB)

Evans, P J; Chu, J W; Johnson, E P; Noorman, J T [Australian Nuclear Science and Technology Organisation, Lucas Heights, NSW (Australia); Sood, D K [Royal Melbourne Inst. of Tech., VIC (Australia)

1994-12-31

Ion implantation is an established method for altering the surface properties of many materials. While a variety of analytical techniques are available for the characterisation of implanted surfaces, those based on particle accelerators such as Rutherford backscattering (RBS) and nuclear reaction analysis (NRA) provide some of the most useful and powerful for this purpose. Application of the latter techniques to metal ion implantation research at ANSTO will be described with particular reference to specific examples from recent studies. Where possible, the information obtained from ion beam analysis will be compared with that derived from other techniques such as Energy Dispersive X-ray (EDX) and Auger spectroscopies. 4 refs., 5 figs.

Ion beam analysis of metal ion implanted surfaces

International Nuclear Information System (INIS)

Evans, P.J.; Chu, J.W.; Johnson, E.P.; Noorman, J.T.; Sood, D.K.

1993-01-01

Ion implantation is an established method for altering the surface properties of many materials. While a variety of analytical techniques are available for the characterisation of implanted surfaces, those based on particle accelerators such as Rutherford backscattering (RBS) and nuclear reaction analysis (NRA) provide some of the most useful and powerful for this purpose. Application of the latter techniques to metal ion implantation research at ANSTO will be described with particular reference to specific examples from recent studies. Where possible, the information obtained from ion beam analysis will be compared with that derived from other techniques such as Energy Dispersive X-ray (EDX) and Auger spectroscopies. 4 refs., 5 figs

Polyatomic ions from a high current ion implanter driven by a liquid metal ion source

Science.gov (United States)

Pilz, W.; Laufer, P.; Tajmar, M.; Böttger, R.; Bischoff, L.

2017-12-01

High current liquid metal ion sources are well known and found their first application as field emission electric propulsion thrusters in space technology. The aim of this work is the adaption of such kind of sources in broad ion beam technology. Surface patterning based on self-organized nano-structures on, e.g., semiconductor materials formed by heavy mono- or polyatomic ion irradiation from liquid metal (alloy) ion sources (LMAISs) is a very promising technique. LMAISs are nearly the only type of sources delivering polyatomic ions from about half of the periodic table elements. To overcome the lack of only very small treated areas by applying a focused ion beam equipped with such sources, the technology taken from space propulsion systems was transferred into a large single-end ion implanter. The main component is an ion beam injector based on high current LMAISs combined with suited ion optics allocating ion currents in the μA range in a nearly parallel beam of a few mm in diameter. Different types of LMAIS (needle, porous emitter, and capillary) are presented and characterized. The ion beam injector design is specified as well as the implementation of this module into a 200 kV high current ion implanter operating at the HZDR Ion Beam Center. Finally, the obtained results of large area surface modification of Ge using polyatomic Bi2+ ions at room temperature from a GaBi capillary LMAIS will be presented and discussed.

Progress in metal ion separation and preconcentration: an overview

International Nuclear Information System (INIS)

Bond, A. H.

1998-01-01

A brief historical perspective covering the most mature chemically-based metal ion separation methods is presented, as is a summary of the recommendations made in the 1987 National Research Council (NRC) report entitled ''Separation and Purification: Critical Needs and Opportunities''. A review of Progress in Metal Ion Separation and Preconcentration shows that advances are occurring in each area of need cited by the NRC. Following an explanation of the objectives and general organization of this book, the contents of each chapter are briefly summarized and some future research opportunities in metal ion separations are presented

Electrospray Ionization Mass Spectrometry: From Cluster Ions to Toxic metal Ions in Biology

Energy Technology Data Exchange (ETDEWEB)

Lentz, Nicholas B. [Iowa State Univ., Ames, IA (United States)

2007-01-01

This dissertation focused on using electrospray ionization mass spectrometry to study cluster ions and toxic metal ions in biology. In Chapter 2, it was shown that primary, secondary and quarternary amines exhibit different clustering characteristics under identical instrument conditions. Carbon chain length also played a role in cluster ion formation. In Chapters 3 and 4, the effects of solvent types/ratios and various instrumental parameters on cluster ion formation were examined. It was found that instrument interface design also plays a critical role in the cluster ion distribution seen in the mass spectrum. In Chapter 5, ESI-MS was used to investigate toxic metal binding to the [Gln¹¹]-amyloid β-protein fragment (1-16). Pb and Cd bound stronger than Zn, even in the presence of excess Zn. Hg bound weaker than Zn. There are endless options for future work on cluster ions. Any molecule that is poorly ionized in positive ion mode can potentially show an increase in ionization efficiency if an appropriate anion is used to produce a net negative charge. It is possible that drug protein or drug/DNA complexes can also be stabilized by adding counter-ions. This would preserve the solution characteristics of the complex in the gas phase. Once in the gas phase, CID could determine the drug binding location on the biomolecule. There are many research projects regarding toxic metals in biology that have yet to be investigated or even discovered. This is an area of research with an almost endless future because of the changing dynamics of biological systems. What is deemed safe today may show toxic effects in the future. Evolutionary changes in protein structures may render them more susceptible to toxic metal binding. As the understanding of toxicity evolves, so does the demand for new toxic metal research. New instrumentation designs and software make it possible to perform research that could not be done in the past. What was undetectable yesterday will

Ion beam induced nanosized Ag metal clusters in glass

International Nuclear Information System (INIS)

Mahnke, H.-E.; Schattat, B.; Schubert-Bischoff, P.; Novakovic, N.

2006-01-01

Silver metal clusters have been formed in soda lime glass by high-energy heavy-ion irradiation at ISL. The metal cluster formation was detected with X-ray absorption spectroscopy (EXAFS) in fluorescence mode, and the shape of the clusters was imaged with transmission electron microscopy. While annealing in reducing atmosphere alone, leads to the formation of metal clusters in Ag-containing glasses, where the Ag was introduced by ion-exchange, such clusters are not very uniform in size and are randomly distributed over the Ag-containing glass volume. Irradiation with 600-MeV Au ions followed by annealing, however, results in clusters more uniform in size and arranged in chains parallel to the direction of the ion beam

Fluorescence signalling of the transition metal ions: Design strategy ...

Indian Academy of Sciences (India)

Unknown

strategy based on the choice of the fluorophore component. N B SANKARAN, S ... skill for the development of fluorosensors of this kind. Further, the ... salts of the transition metal ions have been used for studying the influence of the metal ions.

Metal ion concentrations in body fluids after implantation of hip replacements with metal-on-metal bearing--systematic review of clinical and epidemiological studies.

Directory of Open Access Journals (Sweden)

Albrecht Hartmann

Full Text Available INTRODUCTION: The use of metal-on-metal (MoM total hip arthroplasty (THA increased in the last decades. A release of metal products (i.e. particles, ions, metallo-organic compounds in these implants may cause local and/or systemic adverse reactions. Metal ion concentrations in body fluids are surrogate measures of metal exposure. OBJECTIVE: To systematically summarize and critically appraise published studies concerning metal ion concentrations after MoM THA. METHODS: Systematic review of clinical trials (RCTs and epidemiological studies with assessment of metal ion levels (cobalt, chromium, titanium, nickel, molybdenum in body fluids after implantation of metalliferous hip replacements. Systematic search in PubMed and Embase in January 2012 supplemented by hand search. Standardized abstraction of pre- and postoperative metal ion concentrations stratified by type of bearing (primary explanatory factor, patient characteristics as well as study quality characteristics (secondary explanatory factors. RESULTS: Overall, 104 studies (11 RCTs, 93 epidemiological studies totaling 9.957 patients with measurement of metal ions in body fluids were identified and analyzed. Consistently, median metal ion concentrations were persistently elevated after implantation of MoM-bearings in all investigated mediums (whole blood, serum, plasma, erythrocytes, urine irrespective of patient characteristics and study characteristics. In several studies very high serum cobalt concentrations above 50 µg/L were measured (detection limit typically 0.3 µg/L. Highest metal ion concentrations were observed after treatment with stemmed large-head MoM-implants and hip resurfacing arthroplasty. DISCUSSION: Due to the risk of local and systemic accumulation of metallic products after treatment with MoM-bearing, risk and benefits should be carefully balanced preoperatively. The authors support a proposed "time out" for stemmed large-head MoM-THA and recommend a restricted

Studies on indigenous ion exchange resins: alkali metal ions-hydrogen ion exchange equilibria

International Nuclear Information System (INIS)

Shankar, S.; Kumar, Surender; Venkataramani, B.

2001-01-01

With a view to select a suitable ion exchange resin for the removal of radionuclides (such as cesium, strontium etc.) from low level radioactive effluents, alkali metal ion -H' exchanges on nine indigenous gel- and macroporous-type and nuclear grade resins have been studied at a total ionic strength of 0.1 mol dm .3 (in the case ofCs' -H' exchange it was 0.05 mol dm .3 ). The expected theoretical capacities were not attained by all the resins for the alkali metal ions. The water content (moles/equiv.) of the fully swollen resins for different alkali metal ionic forms do not follow the usual sequence of greater the tendency of the cation to hydrate the higher the water uptake, but a reverse trend. The ion exchange isotherms (plots of equivalent fractions of the ion in resin phase, N M1 to that in solution, N M ) were not satisfactory and sorption of cations, for most of the resins, was possible only when the acidity of the solution was lowered. The variations of the selectivity coefficient, K, with N M show that the resins are highly cross linked and the selectivity sequence: Cs + >K + >Na + >Li + , obtained for all the resins indicate that hydrated ions were involved in the exchange process. However, the increase in the selectivity was not accompanied by the release of water, but unusual uptake of water, during the exchange process. The characteristics of macroporous resins were not significantly different from those of the gel-type resins. The results are discussed in terms of heterogeneity in the polymer net work, improper sulphonation process resulting in the formation of functional groups at inaccessible sites with weak acidic character and the overall lack of control in the preparation of different resins. (author)

Modification of metallic corrosion by ion implantation

International Nuclear Information System (INIS)

Clayton, C.R.

1981-01-01

This review will consider some of the properties of surface alloys, formed by ion implantation, which are effective in modifying corrosion behaviour. Examples will be given of the modification of the corrosion behaviour of pure metals, steels and other engineering alloys, resulting from implantation with metals and metalloids. Emphasis will be given to the modification of anodic processes produced by ion implantation since a review will be given elsewhere in the proceedings concerning the modification of cathodic processes. (orig.)

Adsorption preference for divalent metal ions by Lactobacillus casei JCM1134.

Science.gov (United States)

Endo, Rin; Aoyagi, Hideki

2018-05-09

The removal of harmful metals from the intestinal environment can be inhibited by various ions which can interfere with the adsorption of target metal ions. Therefore, it is important to understand the ion selectivity and adsorption mechanism of the adsorbent. In this study, we estimated the adsorption properties of Lactobacillus casei JCM1134 by analyzing the correlation between its maximum adsorption level (q max ) for seven metals and their ion characteristics. Some metal ions showed altered adsorption levels by L. casei JCM1134 as culture growth time increased. Although it was impossible to identify specific adsorption components, adsorption of Sr and Ba may depend on capsular polysaccharide levels. The maximum adsorption of L. casei JCM1134 (9 h of growth in culture) for divalent metal ions was in the following order: Cu 2+  > Ba 2+  > Sr 2+  > Cd 2+  > Co 2+  > Mg 2+  > Ni 2+ . The q max showed a high positive correlation with the ionic radius. Because this tendency is similar to adsorption occurring through an ion exchange mechanism, it was inferred that an ion exchange mechanism contributed greatly to adsorption by L. casei JCM1134. Because the decrease in the amount of adsorption due to prolonged culture time was remarkable for metals with a large ion radius, it is likely that the adsorption components involved in the ion exchange mechanism decomposed over time. These results and analytical concept may be helpful for designing means to remove harmful metals from the intestinal tract.

Surface modification of metals by ion implantation

International Nuclear Information System (INIS)

Iwaki, Masaya

1988-01-01

Ion implantation in metals has attracted the attention as a useful technology for the formation of new metastable alloys and compounds in metal surface layers without thermal equilibrium. Current studies of metal surface modification by ion implantation with high fluences have expanded from basic research areas and to industrial applications for the improvement of life time of tools. Many results suggest that the high fluence implantation produces the new surface layers with un-expected microscopic characteristics and macroscopic properties due to implant particles, radiation damage, sputtering, and knock-on doping. In this report, the composition, structure and chemical bonding state in surface layers of iron, iron-based alloy and aluminum sheets implanted with high fluences have been investigated by means of secondary ion mass spectroscopy (SIMS), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Tribological properties such as hardness, friction and wear are introduced. (author)

Very broad beam metal ion source for large area ion implantation application

International Nuclear Information System (INIS)

Brown, I.; Anders, S.; Dickinson, M.R.; MacGill, R.A.; Yao, X.

1993-01-01

The authors have made and operated a very broad beam version of vacuum arc ion source and used it to carry out high energy metal ion implantation of a particularly large substrate. A multiple-cathode vacuum arc plasma source was coupled to a 50 cm diameter beam extractor (multiple aperture, accel-decel configuration) operated at a net extraction voltage of up to 50 kV. The metal ion species chosen were Ni and Ta. The mean ion charge state for Ni and Ta vacuum arc plasmas is 1.8 and 2.9, respectively, and so the mean ion energies were up to about 90 and 145 keV, respectively. The ion source was operated in a repetitively pulsed mode with pulse length 250 μs and repetition rate several pulses per second. The extracted beam had a gaussian profile with FWHM about 35 cm, giving a nominal beam area of about 1,000 cm 2 . The current of Ni or Ta metal ions in the beam was up to several amperes. The targets for the ion implantation were a number of 24-inch long, highly polished Cu rails from an electromagnetic rail gun. The rails were located about 80 cm away from the ion source extractor grids, and were moved across a diameter of the vessel in such a way as to maximize the uniformity of the implant along the rail. The saturation retained dose for Ta was limited to about 4 x 10 16 cm -2 because of the rather severe sputtering, in accordance with the theoretical expectations for these implantation conditions. Here they describe the ion source, the implantation procedure, and the kinds of implants that can be produced in this way

Preparation of Dithizone Functionalized Polystyrene for Detecting Heavy Metal Ion

Energy Technology Data Exchange (ETDEWEB)

Shin, Hyeon Ho; Kim, Younghun [Kwangwoon University, Seoul (Korea, Republic of)

2015-04-15

Colorimetric sensors were usually used to detect specific metal ions using selective color change of solutions. While almost organic dye in colorimetric sensors detected single molecule, dithizone (DTZ) solution could be separately detected above 5 kinds of heavy metal ions by the change of clear color. Namely, DTZ could be used as multicolorimetric sensors. However, DTZ was generally used as aqueous type and paper/pellet-type DTZ was not reported yet. Therefore, in this work, polystyrene (PS) was prepared to composite with DTZ and then DTZ/PS pellet was obtained, which was used to selectively detect 10 kinds of heavy metal ions. When 10 ppm of Hg and Co ions was exposed in DTZ/PS pellets, clear color change was revealed. It is noted that DTZ/PS pellet could be used in detecting of heavy metal ion as dry type.

Accumulation of metal ions by pectinates

Science.gov (United States)

Deiana, S.; Deiana, L.; Palma, A.; Premoli, A.; Senette, C.

2009-04-01

The knowledge of the mechanisms which regulate the interactions of metal ions with partially methyl esterified linear polymers of α-1,4 linked D-galacturonic acid units (pectinates), well represented in the root inner and outer apoplasm, is of great relevance to understand the processes which control their accumulation at the soil-root interface as well as their mobilization by plant metabolites. Accumulation of a metal by pectinates can be affected by the presence of other metals so that competition or distribution could be expected depending on the similar or different affinity of the metal ions towards the binding sites, mainly represented by the carboxylate groups. In order to better understand the mechanism of accumulation in the apoplasm of several metal ions, the sorption of Cd(II), Zn(II), Cu(II), Pb(II) and Cr(III) by a Ca-polygalacturonate gel, used as model of the soil-root interface, with a degree of esterification of 18% (PGAE1) and 65% (PGAE2) was studied at pH 3.0, 4.0, 5.0 and 6.0 in the presence of CaCl2 2.5 mM.. The results show that sorption increases with increasing both the initial metal concentration and pH. A similar sorption trend was evidenced for Cu(II) and Pb(II) and for Zn(II) and Cd(II), indicating that the mechanism of sorption for these two ionic couples is quite different. As an example, at pH 6.0 and an initial metal concentration equal to 2.0 mM, the amount of Cu(II) and Pb(II) sorbed was about 1.98 mg-1 of PGAE1 while that of Cd(II) and Zn(II) was about 1.2 mg-1. Cr(III) showed a rather different sorption trend and a much higher amount (2.8 mg-1of PGAE1 at pH 6.0) was recorded. The higher affinity of Cr(III) for the polysaccharidic matrix is attributable to the formation of Cr(III) polynuclear species in solution, as shown by the distribution diagrams obtained through the MEDUSA software. On the basis of these findings, the following affinity towards the PGAE1 can be assessed: Cr(III) > Cu(II) ? Pb(II) > Zn (II) ? Cd

Broad-beam, high current, metal ion implantation facility

International Nuclear Information System (INIS)

Brown, I.G.; Dickinson, M.R.; Galvin, J.E.; Godechot, X.; MacGill, R.A.

1990-07-01

We have developed a high current metal ion implantation facility with which high current beams of virtually all the solid metals of the Periodic Table can be produced. The facility makes use of a metal vapor vacuum arc ion source which is operated in a pulsed mode, with pulse width 0.25 ms and repetition rate up to 100 pps. Beam extraction voltage is up to 100 kV, corresponding to an ion energy of up to several hundred keV because of the ion charge state multiplicity; beam current is up to several Amperes peak and around 10 mA time averaged delivered onto target. Implantation is done in a broad-beam mode, with a direct line-of-sight from ion source to target. Here we describe the facility and some of the implants that have been carried out using it, including the 'seeding' of silicon wafers prior to CVD with titanium, palladium or tungsten, the formation of buried iridium silicide layers, and actinide (uranium and thorium) doping of III-V compounds. 16 refs., 6 figs

Barium isotope fractionation during the experimental transformation of aragonite to witherite and of gypsum to barite, and the effect of ion (de)solvation.

Science.gov (United States)

Böttcher, Michael E; Neubert, Nadja; von Allmen, Katja; Samankassou, Elias; Nägler, Thomas F

2018-06-01

In this study, we present the experimental results for stable barium (Ba) isotope fractionation ( 137 Ba/ 134 Ba) during the transformation of aragonite (CaCO 3 ) and gypsum (CaSO 4 ·2H 2 O) in Ba-bearing aqueous solution to witherite (BaCO 3 ) and barite (BaSO 4 ), respectively. The process was studied at three temperatures between 4 and 60 °C. In all cases, the transformation leads to a relative enrichment of the lighter 134 Ba isotope in the solid compared to the aqueous solution, with 137/134 Ba enrichment factors between -0.11 and -0.17 ‰ for BaCO 3 , and -0.21 and -0.26 ‰ for BaSO 4 . The corresponding mass-dependent 138/134 Ba enrichment factors are -0.15 to -0.23 ‰ for BaCO 3 , and -0.28 to -0.35 ‰ for BaSO 4 . The magnitude of isotope fractionation is within the range of recent reports for witherite and barite formation, as well as trace Ba incorporation into orthorhombic aragonite, and no substantial impact of temperature can be found between 4 and 80 °C. In previous studies, ion (de)solvation has been suggested to impact both the crystallization process of Ba-bearing solids and associated Ba isotope fractionation. Precipitation experiments of BaSO 4 and BaCO 3 using an methanol-containing aqueous solution indicate only a minor effect of ion and crystal surface (de)solvation on the overall Ba isotope fractionation process.

Progress in metal ion separation and preconcentration : an overview.

Energy Technology Data Exchange (ETDEWEB)

Bond, A. H.

1998-05-19

A brief historical perspective covering the most mature chemically-based metal ion separation methods is presented, as is a summary of the recommendations made in the 1987 National Research Council (NRC) report entitled ''Separation and Purification: Critical Needs and Opportunities''. A review of Progress in Metal Ion Separation and Preconcentration shows that advances are occurring in each area of need cited by the NRC. Following an explanation of the objectives and general organization of this book, the contents of each chapter are briefly summarized and some future research opportunities in metal ion separations are presented.

Heavy metal ion adsorption onto polypyrrole-impregnated porous carbon.

Science.gov (United States)

Choi, Moonjung; Jang, Jyongsik

2008-09-01

Polypyrrole-impregnated porous carbon was readily synthesized using vapor infiltration polymerization of pyrrole monomers. The results show that the functionalized polymer layer was successfully coated onto the pore surface of carbon without collapse of mesoporous structure. The modified porous carbon exhibited an improved complexation affinity for heavy metal ions such as mercury, lead, and silver ions due to the amine group of polypyrrole. The introduced polypyrrole layer could provide the surface modification to be applied for heavy metal ion adsorbents. Especially, polymer-impregnated porous carbon has an enhanced heavy metal ion uptake, which is 20 times higher than that of adsorbents with amine functional groups. Furthermore, the relationship between the coated polymer amount and surface area was also investigated in regard to adsorption capacity.

Heavy metal ions are potent inhibitors of protein folding

International Nuclear Information System (INIS)

Sharma, Sandeep K.; Goloubinoff, Pierre; Christen, Philipp

2008-01-01

Environmental and occupational exposure to heavy metals such as cadmium, mercury and lead results in severe health hazards including prenatal and developmental defects. The deleterious effects of heavy metal ions have hitherto been attributed to their interactions with specific, particularly susceptible native proteins. Here, we report an as yet undescribed mode of heavy metal toxicity. Cd 2+ , Hg 2+ and Pb 2+ proved to inhibit very efficiently the spontaneous refolding of chemically denatured proteins by forming high-affinity multidentate complexes with thiol and other functional groups (IC 50 in the nanomolar range). With similar efficacy, the heavy metal ions inhibited the chaperone-assisted refolding of chemically denatured and heat-denatured proteins. Thus, the toxic effects of heavy metal ions may result as well from their interaction with the more readily accessible functional groups of proteins in nascent and other non-native form. The toxic scope of heavy metals seems to be substantially larger than assumed so far

Highly sensitive colour change system within slight differences in metal ion concentrations based on homo-binuclear complex formation equilibrium for visual threshold detection of trace metal ions

International Nuclear Information System (INIS)

Mizuguchi, Hitoshi; Atsumi, Hiroshi; Hashimoto, Keigo; Shimada, Yasuhiro; Kudo, Yuki; Endo, Masatoshi; Yokota, Fumihiko; Shida, Junichi; Yotsuyanagi, Takao

2004-01-01

A new technique of expressing slight differences in metal ion concentrations by clear difference in colour was established for visual threshold detection of trace metal ions. The proposed method is based on rapid change of the mole fraction of the homo-binuclear complex (M 2 L) about a ligand in a narrow range of the total metal ion concentration (M T ) in a small excess, in case the second metal ion is bound to the reagent molecule which can bind two metal ions. Theoretical simulations showed that the highly sensitive colour change within slight differences in metal ion concentrations would be realized under the following conditions: (i) both of the stepwise formation constants of complex species are sufficiently large; (ii) the stepwise formation constant of the 1:1 complex (ML) is larger than that of M 2 L; and (iii) the absorption spectrum of M 2 L is far apart from the other species in the visible region. Furthermore, the boundary of the colour region in M T would be readily controlled by the total ligand concentration (L T ). Based on this theory, the proposed model was verified with the 3,3'-bis[bis(carboxymethyl)amino]methyl derivatives of sulphonephthalein dyes such as xylenol orange (XO), methylthymol blue (MTB), and methylxylenol blue (MXB), which can bind two metal ions at both ends of a π-electron conjugated system. The above-mentioned model was proved with the iron(III)-XO system at pH 2. In addition, MTB and MXB were suitable reagents for the visual threshold detection of trivalent metal ions such as iron(III), aluminium(III), gallium(III) and indium(III) ion in slightly acidic media. The proposed method has been applied successfully as a screening test for aluminium(III) ion in river water sampled at the downstream area of an old mine

Metal ion transport quantified by ICP-MS in intact cells

Science.gov (United States)

Figueroa, Julio A. Landero; Stiner, Cory A.; Radzyukevich, Tatiana L.; Heiny, Judith A.

2016-01-01

The use of ICP-MS to measure metal ion content in biological tissues offers a highly sensitive means to study metal-dependent physiological processes. Here we describe the application of ICP-MS to measure membrane transport of Rb and K ions by the Na,K-ATPase in mouse skeletal muscles and human red blood cells. The ICP-MS method provides greater precision and statistical power than possible with conventional tracer flux methods. The method is widely applicable to studies of other metal ion transporters and metal-dependent processes in a range of cell types and conditions. PMID:26838181

Use of heavy ions to model radiation damage of metals

International Nuclear Information System (INIS)

Shirokov, S.V.; Vyshemirskij, M.P.

2011-01-01

The methods for modeling radiation damage of metals using heavy ions are reviewed and the results obtained are analyzed. It is shown that irradiation of metals with heavy ion can simulate neutron exposure with the equivalent dose with adequate accuracy and permits a detailed analysis of radiation damage of metals

Ion beam assisted deposition of metal-coatings on beryllium

International Nuclear Information System (INIS)

Tashlykov, I.S.; Tul'ev, V.V.

2015-01-01

Thin films were applied on beryllium substrates on the basis of metals (Cr, Ti, Cu and W) with method of the ion-assisted deposition in vacuum. Me/Be structures were prepared using 20 kV ions irradiation during deposition on beryllium neutral fraction generated from vacuum arc plasma. Rutherford back scattering and computer simulation RUMP code were applied to investigate the composition of the modified beryllium surface. Researches showed that the superficial structure is formed on beryllium by thickness ~ 50-60 nm. The covering composition includes atoms of the deposited metal (0.5-3.3 at. %), atoms of technological impurity carbon (0.8-1.8 at. %) and oxygen (6.3-9.9 at. %), atoms of beryllium from the substrate. Ion assisted deposition of metals on beryllium substrate is accompanied by radiation enhanced diffusion of metals, oxygen atoms in the substrate, out diffusion of beryllium, carbon atoms in the deposited coating and sputtering film-forming ions assists. (authors)

Hydrolysis of metal ions. Vol. 1 and 2

Energy Technology Data Exchange (ETDEWEB)

Brown, Paul L. [Geochem Australia, Kiama, NSW (Australia); Ekberg, Christian [Chalmers Univ. of Technology, Goeteborg (Sweden). Nuclear Chemistry/Industrial Materials Recycling

2016-07-01

Filling the need for a comprehensive treatment that covers the theory, methods and the different types of metal ion complexes with water (hydrolysis), this handbook and ready reference is authored by a nuclear chemist from academia and an industrial geochemist. The book includes both cation and anion complexes, and approaches the topic of metal ion hydrolysis by first covering the background, before proceeding with an overview of the dissociation of water and then all different metal-water hydrolysis complexes and compounds. A must-have for scientists in academia and industry working on this interdisciplinary topic.

On the solvation of actinide ions

International Nuclear Information System (INIS)

Hagberg, D.

2007-01-01

Complete text of publication follows: Simulation of the universal ions in water solution is a standardized tool commonly used today. The route to simulation of actinide ions is normally tough because the evaluation of the simulation parameters are normally not given empirically and standard Hartree-Fock calculations are not accurate enough. We use multiconfigurational quantum chemical calculations when deriving the parameters for actinide ion-water potential [1]. The parameters are then simulated using classical molecular dynamics. A case study of the Cm 3+ ion will be presented on the poster. Results from the simulations will be also be discussed, e.g. the radial distribution functions and the coordination number. [1] D. Hagberg, G. Karlstrom, B.O. Roos and L. Gagliardi The coordination of uranyl in water: a combined quantum chemical and molecular simulation study J. Am. Chem. Soc. 127, 14250-14256 (2005)

Charge state of ions scattered by metal surface

International Nuclear Information System (INIS)

Kishinevsky, L.M.; Parilis, E.S.; Verleger, V.K.

1976-01-01

A model for description of charge distributions for scattering of heavy ions in the keV region, on metal surfaces developing and improving the method of Van der Weg and Bierman, and taking into account the connection between the ion charge state and scattering kinematics, is proposed. It is shown that multiple charged particles come from ions with a vacancy in the inner shell while the outer shell vacancies give only single charged ions and neutrals. The approximately linear increase of degree of ionization with normal velocity, and the non-monotonic charge dependence of the energy spectrum established by Chicherov and Buck et al is explained by considering irreversible neutralization in the depth of the metal, taking into account the connection of the charge state with the shape of trajectory and its location relative to the metal surface. The dependence of charge state on surface structure is discussed. Some new experiments are proposed. (author)

Directly relating gas-phase cluster measurements to solution-phase hydrolysis, the absolute standard hydrogen electrode potential, and the absolute proton solvation energy.

Science.gov (United States)

Donald, William A; Leib, Ryan D; O'Brien, Jeremy T; Williams, Evan R

2009-06-08

Solution-phase, half-cell potentials are measured relative to other half-cell potentials, resulting in a thermochemical ladder that is anchored to the standard hydrogen electrode (SHE), which is assigned an arbitrary value of 0 V. A new method for measuring the absolute SHE potential is demonstrated in which gaseous nanodrops containing divalent alkaline-earth or transition-metal ions are reduced by thermally generated electrons. Energies for the reactions 1) M(H(2)O)(24)(2+)(g) + e(-)(g)-->M(H(2)O)(24)(+)(g) and 2) M(H(2)O)(24)(2+)(g) + e(-)(g)-->MOH(H(2)O)(23)(+)(g) + H(g) and the hydrogen atom affinities of MOH(H(2)O)(23)(+)(g) are obtained from the number of water molecules lost through each pathway. From these measurements on clusters containing nine different metal ions and known thermochemical values that include solution hydrolysis energies, an average absolute SHE potential of +4.29 V vs. e(-)(g) (standard deviation of 0.02 V) and a real proton solvation free energy of -265 kcal mol(-1) are obtained. With this method, the absolute SHE potential can be obtained from a one-electron reduction of nanodrops containing divalent ions that are not observed to undergo one-electron reduction in aqueous solution.

Adhesive, abrasive and oxidative wear in ion-implanted metals

International Nuclear Information System (INIS)

Dearnaley, G.

1985-01-01

Ion implantation is increasingly being used to provide wear resistance in metals and cemented tungsten carbides. Field trials and laboratory tests indicate that the best performance is achieved in mild abrasive wear. This can be understood in terms of the classification of wear modes (adhesive, abrasive, oxidative etc.) introduced by Burwell. Surface hardening and work hardenability are the major properties to be enhanced by ion implantation. The implantation of nitrogen or dual implants of metallic and interstitial species are effective. Recently developed techniques of ion-beam-enhanced deposition of coatings can further improve wear resistance by lessening adhesion and oxidation. In order to support such hard coatings, ion implantation of nitrogen can be used as a preliminary treatment. There is thus emerging a versatile group of related hard vacuum treatments involving intense beams of nitrogen ions for the purpose of tailoring metal surfaces to resist wear. (Auth.)

Metal Ion Concentrations in Body Fluids after Implantation of Hip Replacements with Metal-on-Metal Bearing – Systematic Review of Clinical and Epidemiological Studies

Science.gov (United States)

Hartmann, Albrecht; Hannemann, Franziska; Lützner, Jörg; Seidler, Andreas; Drexler, Hans; Günther, Klaus-Peter; Schmitt, Jochen

2013-01-01

Introduction The use of metal-on-metal (MoM) total hip arthroplasty (THA) increased in the last decades. A release of metal products (i.e. particles, ions, metallo-organic compounds) in these implants may cause local and/or systemic adverse reactions. Metal ion concentrations in body fluids are surrogate measures of metal exposure. Objective To systematically summarize and critically appraise published studies concerning metal ion concentrations after MoM THA. Methods Systematic review of clinical trials (RCTs) and epidemiological studies with assessment of metal ion levels (cobalt, chromium, titanium, nickel, molybdenum) in body fluids after implantation of metalliferous hip replacements. Systematic search in PubMed and Embase in January 2012 supplemented by hand search. Standardized abstraction of pre- and postoperative metal ion concentrations stratified by type of bearing (primary explanatory factor), patient characteristics as well as study quality characteristics (secondary explanatory factors). Results Overall, 104 studies (11 RCTs, 93 epidemiological studies) totaling 9.957 patients with measurement of metal ions in body fluids were identified and analyzed. Consistently, median metal ion concentrations were persistently elevated after implantation of MoM-bearings in all investigated mediums (whole blood, serum, plasma, erythrocytes, urine) irrespective of patient characteristics and study characteristics. In several studies very high serum cobalt concentrations above 50 µg/L were measured (detection limit typically 0.3 µg/L). Highest metal ion concentrations were observed after treatment with stemmed large-head MoM-implants and hip resurfacing arthroplasty. Discussion Due to the risk of local and systemic accumulation of metallic products after treatment with MoM-bearing, risk and benefits should be carefully balanced preoperatively. The authors support a proposed „time out“ for stemmed large-head MoM-THA and recommend a restricted indication for hip

Solution thermodynamics of rare-earth metal ions - physicochemical study-

Energy Technology Data Exchange (ETDEWEB)

Amerkhanova, Sh K; Shlyapov, R M; Uali, A S [Buketov Karaganda state university, University str., 28, Karaganda, 100028 (Kazakhstan)], E-mail: amerkhanova_sh@mail.ru

2009-02-01

The results of the studying of interactions in multicomponent systems 'polyvinyl alcohol (PVA) - rare-earth element ion - nitrate of sodium - water' are represented. It is established that for rubidium (I) ions temperature and ionic strength is render destroying action, and for yttrium (III) ions the influence of these factors has return character which is connected with features of an electronic structure of metal ion. It is revealed that a dominating role of non-electrostatic formation composed, hence, the formation of donor-acceptor connection of 'metal - ligand' occurs through atom of oxygen.

Spectroscopic Observation of Water-Mediated Deformation of the CARBOXYLATE-M2+ (M= Mg, Ca) Contact Ion Pair

Science.gov (United States)

Kelleher, Patrick J.; DePalma, Joseph W.; Johnson, Mark

2016-06-01

The binding of alkaline earth dications to the biologically relevant carboxylate ligand has previously been studied using vibrational sum frequency generation (VSFG) spectroscopy of the air-water interface, infrared multiple photon dissociation (IRMPD) spectroscopy of clusters, and DFT methods. These results suggest the presence of both monodentate and bidentate binding motifs of the M2+ ions to the cayboxyl head groups depending on the extent of solvation. We revisit these systems using vibrational predissociation spectroscopy to measure the gas-phase vibrational spectra of the D2-tagged microhydrated [MgOAc(H2O)n=1-5]+ and [CaOAc(H2O)n=1-6]+ clusters. The spectra show that [MgOAc(H2O)n]+ switches from bidentate to monodentate binding promptly at n = 5, while [CaOAc(H2O)n]+ retains its bidentate attachment such that the sixth water molecule initiates the second solvation shell. The difference in binding behavior between these two divalent metal ions is analyzed in the context of the local acidity of the solvent water molecules and the strength of the metal-carboxylate and metal-water interactions. This cluster study provides insight into the chemical physics underlying the unique and surprising impacts of Mg2+ and Ca2+ on the chemistry mediated by sea spray aerosols. Funding for this work was provided by the NSF's Center for Aerosol Impacts on Climate and the Environment.

Accumulation of some metal ions on Bacillus licheniformis

International Nuclear Information System (INIS)

Hafez, M.B.; El-Desouky, W.; Fouad, A.

2001-01-01

Pure species of Bacillus licheniformis was used to remove ions from aqueous and simulated waste solutions. Metal ion accumulation on B. licheniformis was fast. Maximum uptake occurred at pH 4± 0.5 and at 25 ± 3 deg C. One gram of dry B. licheniformis was found to accumulate 115 mg cerium, 34 mg copper and 11 mg cobalt from aqueous solutions. The presence of certain foreign ions such as calcium, sodium and potassium decreased the uptake of ions by B. licheniformis, while citrate and EDTA prevent the uptake. Electron microscopic investigations showed that cerium (III), copper (II) and cobalt (II) accumulated extracellulary around the surface wall of B. licheniformis cells. A bio-adsorption mechanism between the metal ions and B. licheniformis cell wall was proposed. (author)

Ion conducting polymers and polymer blends for alkali metal ion batteries

Science.gov (United States)

DeSimone, Joseph M.; Pandya, Ashish; Wong, Dominica; Vitale, Alessandra

2017-08-29

Electrolyte compositions for batteries such as lithium ion and lithium air batteries are described. In some embodiments the compositions are liquid compositions comprising (a) a homogeneous solvent system, said solvent system comprising a perfluropolyether (PFPE) and polyethylene oxide (PEO); and (b) an alkali metal salt dissolved in said solvent system. In other embodiments the compositions are solid electrolyte compositions comprising: (a) a solid polymer, said polymer comprising a crosslinked product of a crosslinkable perfluropolyether (PFPE) and a crosslinkable polyethylene oxide (PEO); and (b) an alkali metal ion salt dissolved in said polymer. Batteries containing such compositions as electrolytes are also described.

Applications of ion plating in metals fabrication

International Nuclear Information System (INIS)

Bell, R.T.; Thompson, J.C.

1974-01-01

Use of ion plating at the Oak Ridge Y-12 Plant to solve problems encountered in metals fabrication and processing are discussed. Three typical areas are covered. The first is the use of strike coats on various substrates for subsequent electrodeposition. The second area in which ion plating is shown to contribute to a process is in cold welding or room temperature bonding of metals. The third application involves plating U to promote safe handling, fission-product retention, and corrosion protection in nuclear reactors

Cooperative adsorption of critical metal ions using archaeal poly-γ-glutamate.

Science.gov (United States)

Hakumai, Yuichi; Oike, Shota; Shibata, Yuka; Ashiuchi, Makoto

2016-06-01

Antimony, beryllium, chromium, cobalt (Co), gallium (Ga), germanium, indium (In), lithium, niobium, tantalum, the platinoids, the rare-earth elements (including dysprosium, Dy), and tungsten are generally regarded to be critical (rare) metals, and the ions of some of these metals are stabilized in acidic solutions. We examined the adsorption capacities of three water-soluble functional polymers, namely archaeal poly-γ-glutamate (L-PGA), polyacrylate (PAC), and polyvinyl alcohol (PVA), for six valuable metal ions (Co(2+), Ni(2+), Mn(2+), Ga(3+), In(3+), and Dy(3+)). All three polymers showed apparently little or no capacity for divalent cations, whereas L-PGA and PAC showed the potential to adsorb trivalent cations, implying the beneficial valence-dependent selectivity of anionic polyelectrolytes with multiple carboxylates for metal ions. PVA did not adsorb metal ions, indicating that the crucial role played by carboxyl groups in the adsorption of crucial metal ions cannot be replaced by hydroxyl groups under the conditions. In addition, equilibrium studies using the non-ideal competitive adsorption model indicated that the potential for L-PGA to be used for the removal (or collection) of water-soluble critical metal ions (e.g., Ga(3+), In(3+), and Dy(3+)) was far superior to that of any other industrially-versatile PAC materials.

Reactions of metal ions and their clusters in the gas phase using laser ionization: ion cyclotron resonance spectroscopy

International Nuclear Information System (INIS)

Freiser, B.S.

1981-04-01

Two subjects are discussed in this report: advances in proposed studies on metal ion chemistry and expansion of laboratory facilities. The development of a combined pulsed laser source-ion cyclotron resonance spectrometer has proven to be a convenient and powerful method for generating metal ions and for studying their subsequent chemistry in the gas phase. The main emphasis of this research has been on the application of metal ions as a selective chemical ionization reagents and progress in this area are discussed. The goal is to identify trends in reactivity i.e. mechanisms useful in interpreting the chemical ionization spectra of unknown compounds and to test for the functional group selectivity of the various metal ions. The feasibility of these goals have been demonstrated in extensive studies on Cu + with esters and ketones, on Fe + with ethers, ketones, and hydrocarbons, and on Ti + with hydrocarbons. In addition, preliminary results on sulfur containing compounds and on a variety of other metallic ions have been obtained. Laboratory facilities were expanded from one ion cyclotron resonance (ICR) spectrometer to two, plus a third instrument the Fourier Transform Ion Cyclotron Resonance (FTICR) spectrometer

A simple alkali-metal and noble gas ion source for SIMS equipments with mass separation of the primary ions

International Nuclear Information System (INIS)

Duesterhoeft, H.; Pippig, R.

1986-01-01

An alkali-metal ion source working without a store of alkali-metals is described. The alkali-metal ions are produced by evaporation of alkali salts and ionization in a low-voltage arc discharge stabilized with a noble gas plasma or in the case of small alkali-metal ion currents on the base of the well known thermic ionization at a hot tungsten wire. The source is very simple in construction and produces a stable ion current of 0.3 μA for more than 100 h. It is possible to change the ion species in a short time. This source is applicable to all SIMS equipments using mass separation for primary ions. (author)

Crystal structures of two solvates of (18-crown-6potassium acetate

Directory of Open Access Journals (Sweden)

Phil Liebing

2016-12-01

Full Text Available The crystal and molecular strutures of two solvated forms of [K(18c6]OAc (18c6 = 18-crown-6 = 1,4,7,10,13,16-hexaoxacyclooctadecane and OAc = acetate were determined by single-crystal X-ray diffraction, namely (acetato-κ2O,O′(1,4,7,10,13,16-hexaoxacyclooctadecane-κ6Opotassium dihydrate, [K(CH3COO(C12H24O6]·2H2O (1 and (acetato-κ2O,O′aqua(1,4,7,10,13,16-hexaoxacyclooctadecane-κ6Opotassium acetic acid monosolvate [K(CH3COO(C12H24O6(H2O]·CH3COOH (2. In both compounds, the acetate anion is bonded to the potassium ion in a chelating fashion and the metal atom is consequently slightly displaced from the O6 plane of the crown ether. In the crystals, O—H...O hydrogen bonds lead to a polymeric ladder structure in the dihydrate 1, while the acetic acid hydrate 2 features inversion dimers.

Biosorption of heavy metal ions from aqueous solution by red macroalgae.

Science.gov (United States)

Ibrahim, Wael M

2011-09-15

Biosorption is an effective process for the removal and recovery of heavy metal ions from aqueous solutions. The biomass of marine algae has been reported to have high biosorption capacities for a number of heavy metal ions. In this study, four species of red seaweeds Corallina mediterranea, Galaxaura oblongata, Jania rubens and Pterocladia capillacea were examined to remove Co(II), Cd(II), Cr(III) and Pb(II) ions from aqueous solution. The experimental parameters that affect the biosorption process such as pH, contact time and biomass dosage were studied. The maximum biosorption capacity of metal ions was 105.2mg/g at biomass dosage 10 g/L, pH 5 and contact time 60 min. The biosorption efficiency of algal biomass for the removal of heavy metal ions from industrial wastewater was evaluated for two successive cycles. Galaxaura oblongata biomass was relatively more efficient to remove metal ions with mean biosorption efficiency of 84%. This study demonstrated that these seaweeds constitute a promising, efficient, cheap and biodegradable sorbent biomaterial for lowering the heavy metal pollution in the environment. Copyright © 2011 Elsevier B.V. All rights reserved.

Microstructured liquid metal electron and ion sources (MILMES/MILMIS)

Energy Technology Data Exchange (ETDEWEB)

Mitterauer, J [Technische Universitaet Wien (Austria). Institut fuer Allgemeine Elektrotechnik und Elektronik

1997-12-31

Ion or electron beams can be emitted from liquid metal wetted needles, or from capillaries or slits into which the liquid metal is allowed to flow. Large-area liquid metal field emission sources have been proposed recently, using either two-dimensional, regular arrays of cones or capillaries, or even a substrate with an intrinsically microstructured surface covered by a liquid metal film. This latter concept has been realized in a pilot experiment by in situ wicking and wetting of a porous sintered metal disc. Microstructured liquid metal ion or electron sources are capable of operating in a pulsed mode at a current level which is orders of magnitude above that for steady-state operation. (author). 3 figs., 10 refs.

Sparingly Solvating Electrolytes for High Energy Density Lithium-Sulfur Batteries

Energy Technology Data Exchange (ETDEWEB)

Cheng, Lei; Curtiss, Larry A.; Zavadil, Kevin R.; Gewirth, Andrew A.; Shao, Yuyan; Gallagher, Kevin

2016-07-11

Moving to lighter and less expensive battery chemistries compared to lithium-ion requires the control of energy storage mechanisms based on chemical transformations rather than intercalation. Lithium sulfur (Li/S) has tremendous theoretical specific energy, but contemporary approaches to control this solution-mediated, precipitation-dissolution chemistry requires using large excesses of electrolyte to fully solubilize the polysulfide intermediate. Achieving reversible electrochemistry under lean electrolyte operation is the only path for Li/S to move beyond niche applications to potentially transformational performance. An emerging topic for Li/S research is the use of sparingly solvating electrolytes and the creation of design rules for discovering new electrolyte systems that fundamentally decouple electrolyte volume from reaction mechanism. This perspective presents an outlook for sparingly solvating electrolytes as the key path forward for longer-lived, high-energy density Li/S batteries including an overview of this promising new concept and some strategies for accomplishing it.

Solvates of silico-12-molybdic acid with alcohols

International Nuclear Information System (INIS)

Punchuk, I.N.; Chuvaev, V.F.

1984-01-01

With the aim of investigating interaction processes of solid heteropolyacids and organic compounds, solvates are prepared. Solvates are products of adding gaseous methanol, ethanol and isopropanol to silico-12-molybdic acid. The compounds are studied by IR and PMR spectroscopy methods. Possible models for solvate structure are considered, as well as their connection with solvate properties and thermal decomposition

Ultraviolet spectroscopy and metal ions detection

International Nuclear Information System (INIS)

Chaudry, M.A.

1995-01-01

The spectrochemical analysis is based on the interaction of radiation with the chemical species and depends on their nature, having pi, sigma or electrons, or d and f electrons, UV. Visible spectrophotometry has been used extensively in the detection and determination of both organics and inorganics. In UV detection the sensitivity is proportional to the bath length and the excitation coefficient of the given sample. It may be insensitive to many species unless these are converted to UV, absorbing derivatives. The technique has been applied for the monitoring of the effluents from HPLC, as chlorides or other complexes of various elements in this article the utility of HCl as reagent for the spectrophotometric determination of the metal ions like Al(III), As(III,IV), Ba(II), Cd(II), Ca(II) Ce(III), Cs(i), Cr(III,VI), Co(II), Cu(II), Dy(III), Eu(III), Gd(III), Au(III), Hf(IV), Ho(III), In(III), Fe(III), La(III), Pb(II), Lu (III), Mg(II), Mn(II), Hg(II), Mo(VI), Ni(II), Pd(II), Pt(IV), K(I), Pr(III), Re(VII), Ru(IV), Sm(III), Sc(III), Ag(I), Sr(II) Te(III), Th(IV), Sn(II,IV), Ti(III,IV), W(VI), U(VI), V(IV,V), Yb(III), Zn(II) AND Zr(IV) Ions i.e. for meta ions from d of the most of these metal ions has been found sufficient permit their detection in HPLC. Their molar absorptive have also been reported. Reference has also been provided to post column derivatization of some metal ions from d and f block elements for their detection in HPLC. (author) 12 figs.; 6 tabs.; 27 refs

Polyrhodanine modified anodic aluminum oxide membrane for heavy metal ions removal.

Science.gov (United States)

Song, Jooyoung; Oh, Hyuntaek; Kong, Hyeyoung; Jang, Jyongsik

2011-03-15

Polyrhodanine was immobilized onto the inner surface of anodic aluminum oxide (AAO) membrane via vapor deposition polymerization method. The polyrhodanine modified membrane was applied to remove heavy metal ions from aqueous solution because polyrhodanine could be coordinated with specific metal ions. Several parameters such as initial metal concentration, contact time and metal species were evaluated systematically for uptake efficiencies of the fabricated membrane under continuous flow condition. Adsorption isotherms of Hg(II) ion on the AAO-polyrhodanine membrane were analyzed with Langmuir and Freundlich isotherm models. The adsorption rate of Hg(II) ion on the membrane was obeyed by a pseudo-second order equation, indicating the chemical adsorption. The maximum removal capacity of Hg(II) ion onto the fabricated membrane was measured to be 4.2 mmol/g polymer. The AAO-polyrhodanine membrane had also remarkable uptake performance toward Ag(I) and Pb(II) ions. Furthermore, the polyrhodanine modified membrane could be recycled after recovery process. These results demonstrated that the polyrhodanine modified AAO membrane provided potential applications for removing the hazardous heavy metal ions from wastewater. Copyright © 2011 Elsevier B.V. All rights reserved.

Electron spin resonance of the solvation of radiation-produced silver atoms in alcohol-water mixtures

International Nuclear Information System (INIS)

Li, A.S.W.; Kevan, L.

1982-01-01

Frozen solutions of silver salts exposed to 60 Co γ-irradiation form silver atoms by reaction of radiation-produced electrons with the silver ion. At 4 K the silver atoms are initially produced in a nonequilibrium or presolvated state and upon brief thermal excitation to 77 K the first solvation shell geometry changes towards an equilibrium or solvated silver atom. This is most pronounced in water but also occurs in methanol, ethanol and n-propanol matrices. The changes in the electron spin resonance magnetic parameters upon silver atom solvation have been determined. In alcohol-water mixtures Ag 0 is preferentially solvated by polycrystalline water at low alcohol concentration. Above a particular alcohol mole percent Ag 0 suddenly changes its environment to a glassy alcohol one. This sudden change occurs at 17, 13 and 6 mol % methanol, ethanol and n-propanol, respectively. These mole percents correlate with the minimum of the excess enthalpy of mixing and with the hydrogen atom trapping ability of these alcohol-water mixtures. The results also suggest that the local environmental disorder around Ag 0 increases with alcohol chain length in alcohol-water frozen solutions. (author)

Fragmentation study of isolated and nano-solvated biomolecules induced by collision with multiply charged ions and neutral particles

International Nuclear Information System (INIS)

Bernigaud, V.

2009-01-01

This thesis concerns a gas phase study of the fragmentation of bio-molecular systems induced by slow collisions with multiply charged ions (in the keV-region), alkali atoms and rare gases. The main objective was to study the physical processes involved in the dissociation of highly electronically excited systems. In order to elucidate the intrinsic properties of certain biomolecules (porphyrins and amino acids) we have performed experiments in the gas phase with isolated systems. The obtained results demonstrate the high stability of porphyrins after electron removal and attachment. Furthermore, a dependence of the fragmentation pattern produced by multiply charged ions on the isomeric structure of the alanine molecule has been shown. In a second part of the thesis, a strong influence of the environment of the biomolecule on the fragmentation channels, their modification and their new opening, has been clearly proven. This phenomenon occurs in the presence of other surrounding biomolecules (clusters of nucleobases) as well as for molecules of a solvent (molecules of water, methanol and acetonitrile) in which the biomolecule is embedded. In order to extend these studies to larger systems, a new experimental set-up, based on an electro-spray ion source combined with a quadrupole mass filter has been developed. Due to the successful tests and proposed improvements of the device future experiments will become available concerning the fragmentation of large charged and solvated bio-molecular systems induced by collision processes. (author) [fr

Interaction of Hydroxyproline with Bivalent Metal Ions in Chemical ...

African Journals Online (AJOL)

NICO

The stability constants of the ML and ML2 complex species of some metal ions, namely beryllium(II) and cobalt(II), with hydroxyproline were ... metal ions have several significant applications in biological systems.3–20 Beryllium is one ... 1 filter paper for chromatography was used for the purpose of electrophoresis. An Elico ...

Emission of positive oxygen ions from ion bombardment of adsorbate-covered metal surfaces

International Nuclear Information System (INIS)

Kaurin, M.G.

1989-01-01

During ion bombardment of metal surfaces, collision cascades can result in the emission of sputtered secondary ions. Recent experiments, however, have suggested that the emission of positive ions of electronegative adsorbates can result from electronic processes rather than from processes involving elastic collisions. This dissertation presents the results of experiments studying the emission of positive oxygen ions from oxygen- and carbon-monoxide-covered transition metal surfaces during bombardment by 25-250 keV ions of neon, argon, and krypton. The systems studied may be grouped into four categories. For a nickel substrate with adsorbed oxygen, the emission of positive oxygen ions proceeds through collision cascades. For titanium and niobium with adsorbed oxygen, the emission of positive oxygen ions is proportional to the primary ion velocity, consistent with emission from electronic processes; for a given primary ion velocity, the oxygen ion yield is independent of primary ion species. For substrates of molybdenum and tungsten, the oxygen yield is proportional to primary ion velocity, but the yield also depends on the primary ion species for a given primary ion velocity in a manner that is consistent with emission resulting from electronic processes. For these two groups, except for titanium, the yields during neon ion bombardment do not extrapolate (assuming linearity with primary ion velocity) to a nonzero value at zero beam velocity. The magnitude of the oxygen ion yields from these targets is not consistent with that expected if the emission were induced by secondary electrons emitted during the ion bombardment

High-current pulsed ion source for metallic ions

International Nuclear Information System (INIS)

Gavin, B.; Abbott, S.; MacGill, R.; Sorensen, R.; Staples, J.; Thatcher, R.

1981-03-01

A new sputter-ion PIG source and magnet system, optimized for intermediate charge states, q/A of 0.02 to 0.03, is described. This source will be used with the new Wideroe-based injector for the SuperHILAC. Pulsed electrical currents of several emA of heavy metal ions have been produced in a normalized emittance area of .05π cm-mr. The source system is comprised of two electrically separate anode chambers, one in operation and one spare, which can be selected by remote control. The entire source head is small and quickly removable

Some properties of ion and cluster plasma

International Nuclear Information System (INIS)

Gudzenko, L.I.; Derzhiev, V.I.; Yakovlenko, S.I.

1982-01-01

The aggregate of problems connected with the physics of ion and cluster plasma is qualitatively considered. Such a plasma can exist when a dense gas is ionized by a hard ionizer. The conditions for the formation of an ion plasma and the difference between its characteristics and those of an ordinary electron plasma are discussed; a solvated-ion model and the distribution of the clusters with respect to the number of solvated molecules are considered. The recombination rate of the positively and negatively charged clusters is roughly estimated. The parameters of a ball-lightning plasma are estimated on the basis of the cluster model

Alzheimer’s disease: How metal ions define β-amyloid function

DEFF Research Database (Denmark)

Kepp, Kasper Planeta

2017-01-01

focuses on the essential coordination chemistry and biochemistry that relate transition metal ions iron, copper, and zinc to β-amyloid (Aβ) and most likely define the peptide's roles in neurons. The metal-Aβ interactions have elements of both gain of toxic function, as usually considered, but also loss......Alzheimer’s disease is increasingly recognized to be linked to the function and status of metal ions, and recently, the amyloid hypothesis has been strongly intertwined with the metal ion hypothesis; in fact, these two hypotheses fit well together and are not mutually contradictory. This review...... of natural functions, as emphasized in this review. Both these aspects and their relationships are discussed and their implications for future therapeutic strategies are outlined....

Adsorption of heavy metal ions by sawdust of deciduous trees

International Nuclear Information System (INIS)

Bozic, D.; Stankovic, V.; Gorgievski, M.; Bogdanovic, G.; Kovacevic, R.

2009-01-01

The adsorption of heavy metal ions from synthetic solutions was performed using sawdust of beech, linden and poplar trees. The adsorption depends on the process time, pH of the solution, type of ions, initial concentration of metals and the sawdust concentration in suspension. The kinetics of adsorption was relatively fast, reaching equilibrium for less than 20 min. The adsorption equilibrium follows Langmuir adsorption model. The ion exchange mechanism was confirmed assuming that the alkali-earth metals from the adsorbent are substituted by heavy metal ions and protons. On lowering the initial pH, the adsorption capacity decreased, achieving a zero value at a pH close to unity. The maximum adsorption capacity (7-8 mg g -1 of sawdust) was achieved at a pH between 3.5 and 5 for all the studied kinds of sawdust. The initial concentration of the adsorbate and the concentration of sawdust strongly affect the process. No influence of particles size was evidenced. A degree of adsorption higher than 80% can be achieved for Cu 2+ ions but it is very low for Fe 2+ ions, not exceeding 10%.

Effects of complexing compounds on sorption of metal ions to cement

Energy Technology Data Exchange (ETDEWEB)

Loevgren, Lars [Umeaa Univ. (Sweden). Inorganic chemistry

2005-12-15

This present report is a literature review addressing the effects of complexing ligands on the sorption of radionuclides to solid materials of importance for repositories of radioactive waste. Focus is put on laboratory studies of metal ion adsorption to cement in presence of chelating agents under strongly alkaline conditions. As background information, metal sorption to different mineral and cement phases in ligand free systems is described. Furthermore, surface complexation model (SCM) theories are introduced. According to surface complexation theories these interactions occur at specific binding sites at the particle/water interface. Adsorption of cationic metals is stronger at high pH, and the adsorption of anions occurs preferentially at low pH. The adsorption of ions to mineral surfaces is a result of both chemical bonding and electrostatic attraction between the ions and charged mineral surfaces. By combining uptake data with spectroscopic information the sorption can be explained on a molecular level by structurally sound surface complexation models. Most of the metal sorption studies reviewed are dealing with minerals exhibiting oxygen atoms at their surfaces, mainly oxides of Fe(II,III) and Al(III), and aluminosilicates. Investigations of radionuclides are focused on clay minerals, above all montmorillonite and illite. Which mechanism that is governing the metal ion adsorption to a given mineral is to a large extent depending on the metal adsorbed. For instance, sorption of Ni to montmorillonite can occur by formation of inner-sphere mononuclear surface complexes located at the edges of montmorillonite platelets and by formation of a Ni phyllosilicate phase parallel to montmorillonite layers. Also metal uptake to cement materials can occur by different mechanisms. Cationic metals can both be attached to cement (calcium silicate hydrate, CSH) and hardened cement paste (HCP) by formation of inner-sphere complexes at specific surface sites and by

Metal-ion interactions and the structural organization of Sepia eumelanin.

Science.gov (United States)

Liu, Yan; Simon, John D

2005-02-01

The structural organization of melanin granules isolated from ink sacs of Sepia officinalis was examined as a function of metal ion content by scanning electron microscopy and atomic force microscopy. Exposing Sepia melanin granules to ethelenediaminetetraacetic acid (EDTA) solution or to metal salt solutions changed the metal content in the melanin, but did not alter granular morphology. Thus ionic forces between the organic components and metal ions in melanin are not required to sustain the natural morphology once the granule is assembled. However, when aqueous suspensions of Sepia melanin granules of varying metal content are ultra-sonicated, EDTA-washed and Fe-saturated melanin samples lose material to the solution more readily than the corresponding Ca(II) and Mg(II)-loaded samples. The solubilized components are found to be 5,6-dihydroxyindole-2-carboxylic acid (DHICA)-rich constituents. Associated with different metal ions, Na(I), Ca(II) and Mg(II) or Fe(III), these DHICA-rich entities form distinct two-dimensional aggregation structures when dried on the flat surface of mica. The data suggest multiply-charged ions play an important role in assisting or templating the assembly of the metal-free organic components to form the three-dimensional substructure distributed along the protein scaffold within the granule.

Computational solvation analysis of biomolecules in aqueous ionic liquid mixtures : From large flexible proteins to small rigid drugs.

Science.gov (United States)

Zeindlhofer, Veronika; Schröder, Christian

2018-06-01

Based on their tunable properties, ionic liquids attracted significant interest to replace conventional, organic solvents in biomolecular applications. Following a Gartner cycle, the expectations on this new class of solvents dropped after the initial hype due to the high viscosity, hydrolysis, and toxicity problems as well as their high cost. Since not all possible combinations of cations and anions can be tested experimentally, fundamental knowledge on the interaction of the ionic liquid ions with water and with biomolecules is mandatory to optimize the solvation behavior, the biodegradability, and the costs of the ionic liquid. Here, we report on current computational approaches to characterize the impact of the ionic liquid ions on the structure and dynamics of the biomolecule and its solvation layer to explore the full potential of ionic liquids.

Infrared spectroscopy of model electrochemical interfaces in ultrahigh vacuum: some implications for ionic and chemisorbate solvation at electrode surfaces

Science.gov (United States)

Villegas, Ignacio; Kizhakevariam, Naushad; Weaver, Michael J.

1995-07-01

The utility of infrared reflection-absorption spectroscopy (IRAS) for examining structure and bonding for model electrochemical interfaces in ultrahigh vacuum (UHV) is illustrated, focusing specifically on the solvation of cations and chemisorbed carbon monoxide on Pt(111). These systems were chosen partly in view of the availability of IRAS data (albeit limited to chemisorbate vibrations) for the corresponding in-situ metal-solution interfaces, enabling direct spectral comparisons to be made with the "UHV electrochemical model" systems. Kelvin probe measurements of the metal-UHV surface potential changes (ΔΦ) attending alterations in the interfacial composition are also described: these provide the required link to the in-situ electrode potentials as well as yielding additional insight into surface solvation. Variations in the negative electronic charge density and, correspondingly, in the cation surface concentration (thereby mimicking charge-induced alterations in the electrode potential below the potential of zero charge) are achieved by potassium atom dosage onto Pt(111). Of the solvents selected for discussion here — deuterated water, methanol, and acetonitrile — the first two exhibit readily detectable vibrational bands which provide information on the ionic solvation structure. Progressively dosing these solvents onto Pt(111) in the presence of low potassium coverages yields marked alterations in the solvent vibrational bands which can be understood in terms of sequential cation solvation. Comparison between these spectra for methanol with analogous data for sequential methanol solvation of gas-phase alkali cations enables the influence of the interfacial environment to be assessed. The effects of solvating chemisorbed CO are illustrated for acetonitrile; the markedly larger shifts in CO frequencies and binding sites for dilute CO adlayers can be accounted for in terms of short-range coadsorbate interactions in addition to longer-range Stark effects

Defect-impurity interactions in ion-implanted metals

International Nuclear Information System (INIS)

Turos, A.

1986-01-01

An overview of defect-impurity interactions in metals is presented. When point defects become mobile they migrate towards the sinks and on the way can be captured by impurity atoms forming stable associations so-called complexes. In some metallic systems complexes can also be formed athermally during ion implantation by trapping point defects already in the collision cascade. An association of a point defect with an impurity atom leads to its displacement from the lattice site. The structure and stability of complexes are strongly temperature dependent. With increasing temperature they dissociate or grow by multiple defect trapping. The appearance of freely migrating point defects at elevated temperatures, due to ion bombardment or thermal annealing, causes via coupling with defect fluxes, important impurity redistribution. Because of the sensitivity of many metal-in-metal implanted systems to radiation damage the understanding of this processes is essential for a proper interpretation of the lattice occupancy measurements and the optimization of implantation conditions. (author)

Metal ion interaction of an oligopeptide fragment representing the regulatory metal binding site of a CueR protein

DEFF Research Database (Denmark)

Jancsó, Attila; Szokolai, Hajnalka; Roszahegyi, Livia

2013-01-01

Metalloregulatory proteins of the MerR family are transcriptional activators that sense/control the concentration of various metal ions inside bacteria.1 The Cu+ efflux regulator CueR, similarly to other MerR proteins, possesses a short multiple Cys-containing metal binding loop close to the C...... of cognate metal ions.2 Nevertheless, it is an interesting question whether the same sequence, when removed from the protein, shows a flexibility to adopt different coordination environments and may efficiently bind metal ions having preferences for larger coordination numbers....

Heavy metal ion uptake properties of polystyrene-supported ...

Indian Academy of Sciences (India)

Unknown

concentration on the uptake of metal ions have been studied. The uptake ... employed for the removal of heavy metal pollutants from industrial waste water. ... nitrate, mercuric chloride, cadmium nitrate and potassium dichromate salts. ... polymer resin was determined by reacting 50, 100, 150, 200, 250 and 300 ppm of metal.

Investigation of metal ions in fusion plasmas using emission spectroscopy

International Nuclear Information System (INIS)

Tale, I.

2005-01-01

Full text: The Latvian and Portugal Associations are performing development of advanced plasma - facing system using the liquid metal limiter. The objectives of this project require study of the influence of the liquid metal limiter on the main plasma parameters, including concentration of evaporated metal atoms in plasma. The fusion plasmas are related to the dense hot plasmas. The required average ion temperature according to the ITER project (International Thermonuclear Experimental Reactor) is 8,0 keV (9,3 x 10 7 0 K), the average electron temperature - 8,9 keV (1,04 x 10 8 0 K). Plasma temperature operated in the research tokamak ISSTOK, involved in testing of liquid metal limiter concept is considerably less, being of order of 10 50 K. The ionization degree of metal atoms considerably depends on the plasma ion temperature. Density of metal vapours in plasma can be estimated using the following two spectroscopic methods: The fluorescence of the multiple ionised metal ions in steady state concentration; The charge exchange emission during ionisation of evaporated metal ions. In the first step of development of testing system of metal vapours the equipment and instrumentation for charge exchange spectroscopy of Ga and In has been elaborated taking into account the following features of plasma emission. The Ga emission lines occur on the background high temperature plasma black body emission and stray light. Radial distribution of Ga in plasma in the facing plane of Ga flux is desirable

Ion Correlation Effects in Salt-Doped Block Copolymers

Science.gov (United States)

Brown, Jonathan R.; Seo, Youngmi; Hall, Lisa M.

2018-03-01

We apply classical density functional theory to study how salt changes the microphase morphology of diblock copolymers. Polymers are freely jointed and one monomer type favorably interacts with ions, to account for the selective solvation that arises from different dielectric constants of the microphases. By including correlations from liquid state theory of an unbound reference fluid, the theory can treat chain behavior, microphase separation, ion correlations, and preferential solvation, at the same coarse-grained level. We show good agreement with molecular dynamics simulations.

Application of monocarboxylic acids for the extraction of metal ions-literature survey

International Nuclear Information System (INIS)

Brzozka, Z.; Rozycki, C.

1980-01-01

In the paper there is presented a literature review concerning the application of monocarboxylic acids for extraction of metal ions. The following problems are discussed: characteristic of monocarboxylic acids and their mixtures, the equilibria between the acid solution in organic solvent and aqueous phase, the mechanism of acid partition, complexes of carboxylic acids and metal ions in aqueous phase, mechanism of extraction by means of carboxylic acids as well as the problems concerning the extraction of individual metal ions. Data about the extraction of metal ions are presented in table. The 138 references are given. (author)

Uptake of metal ions by a silica-based tetraphenylporphyrin sorbent

Energy Technology Data Exchange (ETDEWEB)

Pyrzynska, K.; Sadowska, M.; Trojanowicz, M.

1999-09-01

The [5-p-carboxyphenyl-10,15,20-triphenyl]porphyrin (TPP) covalently attached to aminopropyl silica gel was examined with respect to the sorption of transition metal ions. The distribution coefficients (K{sub d}) are reported for some metal ions with this new sorbent as a function of pH. It was found that in optimum pH conditions the sorption of Cu(II) and Fe(III) is much faster than that of Co(II) and Cr(III). The binding of metal ions is strongly affected by the presence of various species accelerating the complex formation. The application of porphyrin ligands for preconcentration and metal-matrix separation was also examined using complex formation in solution coupled with an anion exchange resin and column chelation procedure, e.g. sorption of metal on an anion exchanger previously loaded with tetra(4-carboxyphenyl)porphyrin.

Coordination of cassava starch to metal ions and thermolysis of ...

African Journals Online (AJOL)

Cassava starch formed Werner-type complexes with ions of metals from the transition groups. This was proven by conductivity and electron paramagnetic resonance measurements. The coordination of starch to central metal ions influenced the thermal decomposition of starch. As a rule complexes started to decompose at ...

Hybrid Quantum Mechanics/Molecular Mechanics Solvation Scheme for Computing Free Energies of Reactions at Metal-Water Interfaces.

Science.gov (United States)

Faheem, Muhammad; Heyden, Andreas

2014-08-12

We report the development of a quantum mechanics/molecular mechanics free energy perturbation (QM/MM-FEP) method for modeling chemical reactions at metal-water interfaces. This novel solvation scheme combines planewave density function theory (DFT), periodic electrostatic embedded cluster method (PEECM) calculations using Gaussian-type orbitals, and classical molecular dynamics (MD) simulations to obtain a free energy description of a complex metal-water system. We derive a potential of mean force (PMF) of the reaction system within the QM/MM framework. A fixed-size, finite ensemble of MM conformations is used to permit precise evaluation of the PMF of QM coordinates and its gradient defined within this ensemble. Local conformations of adsorbed reaction moieties are optimized using sequential MD-sampling and QM-optimization steps. An approximate reaction coordinate is constructed using a number of interpolated states and the free energy difference between adjacent states is calculated using the QM/MM-FEP method. By avoiding on-the-fly QM calculations and by circumventing the challenges associated with statistical averaging during MD sampling, a computational speedup of multiple orders of magnitude is realized. The method is systematically validated against the results of ab initio QM calculations and demonstrated for C-C cleavage in double-dehydrogenated ethylene glycol on a Pt (111) model surface.

Metal is not inert: role of metal ions released by biocorrosion in aseptic loosening--current concepts.

Science.gov (United States)

Cadosch, Dieter; Chan, Erwin; Gautschi, Oliver P; Filgueira, Luis

2009-12-15

Metal implants are essential therapeutic tools for the treatment of bone fractures and joint replacements. The metals and metal alloys used in contemporary orthopedic and trauma surgery are well tolerated by the majority of patients. However, complications resulting from inflammatory and immune reactions to metal implants have been well documented. This review briefly discusses the different mechanisms of metal implant corrosion in the human body, which lead to the release of significant levels of metal ions into the peri-implant tissues and the systemic blood circulation. Additionally, this article reviews the effects of the released ions on bone metabolism and the immune system and discusses their involvement in the pathophysiological mechanisms of aseptic loosening and metal hypersensitivity in patients with metal implants.

Real-time detection of metal ions using conjugated polymer composite papers.

Science.gov (United States)

Lee, Ji Eun; Shim, Hyeon Woo; Kwon, Oh Seok; Huh, Yang-Il; Yoon, Hyeonseok

2014-09-21

Cellulose, a natural polymeric material, has widespread technical applications because of its inherent structural rigidity and high surface area. As a conjugated polymer, polypyrrole shows practical potential for a diverse and promising range of future technologies. Here, we demonstrate a strategy for the real-time detection and removal of metal ions with polypyrrole/cellulose (PPCL) composite papers in solution. Simply, the conjugated polymer papers had different chemical/physical properties by applying different potentials to them, which resulted in differentiable response patterns and adsorption efficiencies for individual metal ions. First, large-area PPCL papers with a diameter of 5 cm were readily obtained via vapor deposition polymerization. The papers exhibited both mechanical flexibility and robustness, in which polypyrrole retained its redox property perfectly. The ability of the PPCL papers to recognize metal ions was examined in static and flow cells, in which real-time current change was monitored at five different applied potentials (+1, +0.5, 0, -0.5, and -1 V vs. Ag/AgCl). Distinguishable signals in the PPCL paper responses were observed for individual metal ions through principal component analysis. Particularly, the PPCL papers yielded unique signatures for three metal ions, Hg(ii), Ag(i), and Cr(iii), even in a real sample, groundwater. The sorption of metal ions by PPCL papers was examined in the flow system. The PPCL papers had a greatly superior adsorption efficiency for Hg(ii) compared to that of the other metal ions. With the strong demand for the development of inexpensive, flexible, light-weight, and environmentally friendly devices, the fascinating characteristics of these PPCL papers are likely to provide good opportunities for low-cost paper-based flexible or wearable devices.

Separation of strontium ions from other alkaline earth metal ions using masking reagent

International Nuclear Information System (INIS)

Komatsu, Y.

1996-01-01

Cs + and Sr 2+ have been well known as serious elements in high level radioactive waste. Separation of Cs + has already been successful when using an ion-exchange method from solution in the presence of other alkali metal ions. The separation of Sr 2+ is, however, not so easy by any known separation method such as solvent-extraction and ion-exchange methods. This is because Sr 2+ is in the middle of the selectivity series, which is Mg 2+ > Ca 2+ > Sr 2+ > Ba 2+ for the solvent-extraction method and Ba 2+ > Sr 2+ > Ca 2+ > Mg 2+ for the ion- exchange method. In the present study, separation of strontium from other alkaline earth metal ions was studied by a combined use of three types of separation methods at 298 K: the solvent-extraction method was applied for the first separation, in which thenoyltrifluoroacetone (TTA, extractant) and trioctylphosphine oxide ( TOPO, adduct forming ligand) were used for the organic phase of the system. The separation factors for each combination of four alkaline earth metal ions were determined by the values of the distribution ratio. The Mg 2+ was well separated from Sr 2+ by the TTA-TOPO system. However, the separation of the combinations of Ca 2+ -Sr 2+ and Sr 2+ -Ba 2+ was not complete by the above solvent-extraction system. The second separation method, an ion-exchange method was applied using dihydrogen tetratitanate hydrate fibers (H 2 Ti 4 O 9 nH 2 O) as an ion exchanger to separate Sr 2+ and Ba 2+ . The separation factors for each combination of four alkaline earth metal ions were calculated by the values of the distribution coefficients. Ba 2+ was well separated from Sr 2+ by the ion-exchange method. To separate Ca 2+ and Sr 2+ , however, a modified solvent-extraction method was finally used in which H 2 Ti 4 O 9 nH 2 O was used as a masking reagent of Sr 2+ . After the dihydrogen tetratitanate hydrate fibers were contacted with the aqueous solution containing Ca 2+ and Sr 2+ , the organic solution containing TTA and TOPO

Development of a method employing chitosan to remove metallic ions from wastewater

International Nuclear Information System (INIS)

Janegitz, Bruno Campos; Lourencao, Bruna Claudia; Lupetti, Karina Omuro; Fatibello-Filho, Orlando

2007-01-01

In this work a method was developed for removing metallic ions from wastewaters by co-precipitation of Cu 2+ , Pb 2+ , Cd 2+ , Cr 3+ and Hg 2+ with chitosan and sodium hydroxide solution. Solutions of these metallic ions in the range from 0.55 to 2160 mg L -1 were added to chitosan dissolved in 0.05 mol L -1 HCl. For the co-precipitation of metal-chitosan-hydroxide a 0.17 mol L -1 NaOH solution was added until pH 8.5-9.5. A parallel study was carried out applying a 0.17 mol L -1 NaOH solution to precipitate those metallic ions. Also, a chitosan solid phase column was used for removing those metallic ions from wastewaters. (author)

Kinetic study of heavy metal ions removal by ion exchange in batch conical air spouted bed

Directory of Open Access Journals (Sweden)

T.M. Zewail

2015-03-01

Full Text Available Spouted bed contactor is a hybrid of fixed and fluidized bed contactors, which retains the advantages of each with good hydrodynamic conditions. The aim of the present study is to investigate the performance of a batch conical air spouted vessel for heavy metal removal by strong cation exchange resins (AMBERJET 1200 Na. The effect of various parameters such as type of heavy metal ions (Ni+2 and Pb+2, contact time, superficial air velocity and initial heavy metal ion concentration on % heavy metal ion removal has been investigated. It has been found that under optimum conditions 98% and 99% removal of Ni+2 and Pb+2 were achieved respectively. Several kinetic models were used to test the experimental data and to examine the controlling mechanism of the sorption process. The present results of Ni+2 and Pb+2 well fit pseudo second order kinetic model with a high correlation coefficient. Both film diffusion and intra-particle diffusion contribute to the ion exchange process. The present study revealed that spouted bed vessel may provide an effective alternative for conducting ion exchange reactions.

The inhibition of positronium by the chloride ion in water and the positron: Chloride reaction

International Nuclear Information System (INIS)

Beling, C.D.; Smith, F.A.

1983-01-01

A discussion is made of existing theories of Ps inhibition in the presence of Cl - ions. Our favoured interpretation of the data uses the thermalised pre-solvated positron as a common precursor of Ps and e + Cl - . Consideration is given to the prevention of solvation by the strong electric fields in the vicinity of Cl - ions, assuming best estimates for the solvation time, positron mobility and intermolecular spacing. An expression for the Ps inhibition constant K is derived on the basis of diffusive capture. The observed enhancement of Ps yield at higher Cl - concentrations is attributed to the scavenging by the Cl - ion of highly mobile species such as H 2 + O within times approx.=10 -14 s. Dissociation between e + Cl - and the solvated state esub(s) + is suggested as the cause of the ''missing fraction''. (orig.)

MCTBI: a web server for predicting metal ion effects in RNA structures.

Science.gov (United States)

Sun, Li-Zhen; Zhang, Jing-Xiang; Chen, Shi-Jie

2017-08-01

Metal ions play critical roles in RNA structure and function. However, web servers and software packages for predicting ion effects in RNA structures are notably scarce. Furthermore, the existing web servers and software packages mainly neglect ion correlation and fluctuation effects, which are potentially important for RNAs. We here report a new web server, the MCTBI server (http://rna.physics.missouri.edu/MCTBI), for the prediction of ion effects for RNA structures. This server is based on the recently developed MCTBI, a model that can account for ion correlation and fluctuation effects for nucleic acid structures and can provide improved predictions for the effects of metal ions, especially for multivalent ions such as Mg 2+ effects, as shown by extensive theory-experiment test results. The MCTBI web server predicts metal ion binding fractions, the most probable bound ion distribution, the electrostatic free energy of the system, and the free energy components. The results provide mechanistic insights into the role of metal ions in RNA structure formation and folding stability, which is important for understanding RNA functions and the rational design of RNA structures. © 2017 Sun et al.; Published by Cold Spring Harbor Laboratory Press for the RNA Society.

The ion implantation of metals and engineering materials

International Nuclear Information System (INIS)

Dearnaley, G.

1978-01-01

An entirely new method of metal finishing, by the process of ion implantation, is described. Introduced at first for semiconductor device applications, this method has now been demonstrated to produce major and long-lasting improvements in the durability of material surfaces, as regards both wear and corrosion. The process is distinct from that of ion plating, and it is not a coating technique. After a general description of ion implantation examples are given of its effects on wear behaviour (mostly in steels and cemented carbides) and on corrosion, in a variety of metals and alloys. Its potential for producing decorative finishes is mentioned briefly. The equipment necessary for carrying out ion implantation for engineering applications has now reached the prototype stage, and manufacture of plant for treating a variety of tools and components is about to commence. These developments are outlined. (author)

Metal ion binding with dehydroannulenes – Plausible two ...

Indian Academy of Sciences (India)

WINTEC

Theoretical investigations have been carried out at B3LYP/6-311++G** level of theory to study the binding ... Alkali metals; dehydroannulenes; binding energy; penetration barrier. 1. .... can be discriminated from larger metal ions by running.

Metal negative ion beam extraction from a radio frequency ion source

Energy Technology Data Exchange (ETDEWEB)

Kanda, S.; Yamada, N.; Kasuya, T.; Romero, C. F. P.; Wada, M.

2015-04-08

A metal ion source of magnetron magnetic field geometry has been designed and operated with a Cu hollow target. Radio frequency power at 13.56 MHz is directly supplied to the hollow target to maintain plasma discharge and induce self-bias to the target for sputtering. The extraction of positive and negative Cu ion beams have been tested. The ion beam current ratio of Cu{sup +} to Ar{sup +} has reached up to 140% when Ar was used as the discharge support gas. Cu{sup −} ion beam was observed at 50 W RF discharge power and at a higher Ar gas pressure in the ion source. Improvement of poor RF power matching and suppression of electron current is indispensable for a stable Cu{sup −} ion beam production from the source.

Ion-induced effects on metallic nanoparticles

International Nuclear Information System (INIS)

Klimmer, Andreas

2010-01-01

This work deals with the ion-irradiation of metallic nanoparticles in combination with various substrates. Particle diameters were systematically varied within the range of 2.5-14 nm, inter-particle distances range from 30-120 nm. Irradiations were performed with various inert gas ions with energies of 200 keV, resulting in an average ion range larger than the particle dimensions and therefore the effects of irradiation are mainly due to creation of structural defects within the particles and the underlying substrate as well. The main part of this work deals with ion-induced burrowing of metallic nanoparticles into the underlying substrate. The use of micellar nanoparticles with sharp size distribution combined with AFM and TEM analysis allows a much more detailed look at this effect than other works on that topic so far. With respect to the particle properties also a detailed look on the effect of irradiation on the particle structure would be interesting, which might lead to a deliberate influence on magnetic properties, for example. Within the context of this work, first successful experiments were performed on FePt particles, showing a significant reduction of the ordering temperature leading to the magnetically interesting, ordered L1 0 phase. (orig.)

Adaptation of metal arc plasma source to plasma source ion implantation

International Nuclear Information System (INIS)

Shamim, M.M.; Fetherston, R.P.; Conrad, J.R.

1995-01-01

In Plasma Source Ion Implantation (PSII) a target is immersed in a plasma and a train of high negative voltage pulses is applied to accelerate ions into the target and to modify the properties in the near surface region. In PSII, until now the authors have been using gaseous species to generate plasmas. However metal ion plasma may be used to modify the surface properties of material for industrial applications. Conventionally the ion implantation of metal ions is performed using beam line accelerators which have complex engineering and high cost. The employment of a metal arc source to PSII has tremendous potential due to its ability to process the conformal surfaces, simple engineering and cost effectiveness. They have installed metal arc source for generation of titanium plasma. Currently, they are investigating the properties of titanium plasma and material behavior of titanium implanted aluminum and 52100 steel. The recent results of this investigation are presented

Solvation of hydrocarbons in aqueous-organic mixtures

International Nuclear Information System (INIS)

Sedov, I.A.; Magsumov, T.I.; Solomonov, B.N.

2016-01-01

Highlights: • Thermodynamic functions of solvation in mixtures of water with acetone and acetonitrile are measured at T = 298.15 K. • Solvation of n-octane and toluene in aqueous-organic mixtures is studied. • When increasing water content, Gibbs free energies grow up steadily, while enthalpies have a maximum. • Hydrocarbons are preferentially solvated with organic cosolvent even in mixtures with rather high water content. • Acetonitrile suppresses the hydrophobic effect less than acetone. - Abstract: We study the solvation of two hydrocarbons, n-octane and toluene, in binary mixtures of water with organic cosolvents. Two polar aprotic cosolvents that are miscible with water in any proportions, acetonitrile and acetone, were considered. We determine the magnitudes of thermodynamic functions of dissolution and solvation at T = 298.15 K in the mixtures with various compositions. Solution calorimetry was used to measure the enthalpies of solution, and GC headspace analysis was applied to obtain limiting activity coefficients of solutes in the studied systems. For the first time, the enthalpies of solution of alkane in the mixtures with high water content were measured directly. We observed well-pronounced maxima of the dependencies of enthalpies of solvation from the composition of solvent and no maxima for the Gibbs free energies of solvation. Two factors are concluded to be important to explain the observed tendencies: high energy cost of reorganization of binary solvent upon insertion of solute molecules and preferential surrounding of hydrocarbons with the molecules of organic cosolvent. Enthalpy-entropy compensation leads to a steady growth of the Gibbs free energies with increasing water content. On the other hand, consideration of the plots of the Gibbs free energy against enthalpy of solvation clearly shows that the solvation properties are changed dramatically after addition of a rather small amount of organic cosolvents. It is shown that they

Spectroscopic and computational studies of ionic clusters as models of solvation and atmospheric reactions

Science.gov (United States)

Kuwata, Keith T.

Ionic clusters are useful as model systems for the study of fundamental processes in solution and in the atmosphere. Their structure and reactivity can be studied in detail using vibrational predissociation spectroscopy, in conjunction with high level ab initio calculations. This thesis presents the applications of infrared spectroscopy and computation to a variety of gas-phase cluster systems. A crucial component of the process of stratospheric ozone depletion is the action of polar stratospheric clouds (PSCs) to convert the reservoir species HCl and chlorine nitrate (ClONO2) to photochemically labile compounds. Quantum chemistry was used to explore one possible mechanism by which this activation is effected: Cl- + ClONO2 /to Cl2 + NO3- eqno(1)Correlated ab initio calculations predicted that the direct reaction of chloride ion with ClONO2 is facile, which was confirmed in an experimental kinetics study. In the reaction a weakly bound intermediate Cl2-NO3- is formed, with ~70% of the charge localized on the nitrate moiety. This enables the Cl2-NO3- cluster to be well solvated even in bulk solution, allowing (1) to be facile on PSCs. Quantum chemistry was also applied to the hydration of nitrosonium ion (NO+), an important process in the ionosphere. The calculations, in conjunction with an infrared spectroscopy experiment, revealed the structure of the gas-phase clusters NO+(H2O)n. The large degree of covalent interaction between NO+ and the lone pairs of the H2O ligands is contrasted with the weak electrostatic bonding between iodide ion and H2O. Finally, the competition between ion solvation and solvent self-association is explored for the gas-phase clusters Cl/-(H2O)n and Cl-(NH3)n. For the case of water, vibrational predissociation spectroscopy reveals less hydrogen bonding among H2O ligands than predicted by ab initio calculations. Nevertheless, for n /ge 5, cluster structure is dominated by water-water interactions, with Cl- only partially solvated by the

Relative Free Energies for Hydration of Monovalent Ions from QM and QM/MM Simulations.

Science.gov (United States)

Lev, Bogdan; Roux, Benoît; Noskov, Sergei Yu

2013-09-10

Methods directly evaluating the hydration structure and thermodynamics of physiologically relevant cations (Na(+), K(+), Cl(-), etc.) have wide ranging applications in the fields of inorganic, physical, and biological chemistry. All-atom simulations based on accurate potential energy surfaces appear to offer a viable option for assessing the chemistry of ion solvation. Although MD and free energy simulations of ion solvation with classical force fields have proven their usefulness, a number of challenges still remain. One of them is the difficulty of force field benchmarking and validation against structural and thermodynamic data obtained for a condensed phase. Hybrid quantum mechanical/molecular mechanical (QM/MM) models combined with sampling algorithms have the potential to provide an accurate solvation model and to incorporate the effects from the surrounding, which is often missing in gas-phase ab initio computations. Herein, we report the results from QM/MM free energy simulations of Na(+)/K(+) and Cl(-)/Br(-) hydration where we simultaneously characterized the relative thermodynamics of ion solvation and changes in the solvation structure. The Flexible Inner Region Ensemble Separator (FIRES) method was used to impose a spatial separation between QM region and the outer sphere of solvent molecules treated with the CHARMM27 force field. FEP calculations based on QM/MM simulations utilizing the CHARMM/deMon2k interface were performed with different basis set combinations for K(+)/Na(+) and Cl(-)/Br(-) perturbations to establish the dependence of the computed free energies on the basis set level. The dependence of the computed relative free energies on the size of the QM and MM regions is discussed. The current methodology offers an accurate description of structural and thermodynamic aspects of the hydration of alkali and halide ions in neat solvents and can be used to obtain thermodynamic data on ion solvation in condensed phase along with underlying

Adsorption of heavy metal ions by activated charcoal

International Nuclear Information System (INIS)

Fujikawa, Mitsuo

1978-01-01

The adsorption effect was measured for several kinds of heavy metal ions, Pb 2+ , Cd 2+ , Cu 2+ and Zn 2+ by passing them through activated charcoal beds and changing the pH values of solutions. The test procedure is to keep the pH value of solution more than 10 at first, filter heavy metal hydroxide deposit, measure the remaining ion concentration in filtrate, and also test the influence of the addition of alkali to each kind of ions. The individual test procedure for each kind of ions is explained. As for the Cd ions, after the detailed experimental procedure is explained, the adsorption characteristic line is shown as the relation between the adsorption quantity and the equilibrium concentration of Cd 2+ . The similar test procedure and the adsorption characteristic lines are shown and evaluated about Pb 2+ , Cu 2+ and Zn 2+ . These lines are all linear, but have different adsorption quantity and inclination in relation to heavy metal ion concentration. Concerning the influence of pH to adsorption, the characteristics of pH increase are presented, when alkali is added by various quantities to Zn 2+ , Cu 2+ , Pb 2+ and Cd 2+ . The pH of Pb 2+ increased to about 10 by adding 0.4 cc alkali and saturates, but the pH of the other ions did not saturate by adding less than 1.5 cc alkali. When the water containing heavy metals are treated, Cd 2+ , Pb 2+ , Cu 2+ and Zn 2+ are removed almost satisfactorily by passing them through active charcoal filters and keeping pH at 10. The experimental concentrations are 0.05 ppm at pH 10 in Cd, 0.86 ppm at 10.3 in Pb, 0 ppm at pH 9.6 in Cu, 0.06 ppm at pH 8.8 and 12.4 ppm at pH 9.8 in Zn. (Nakai, Y.)

Fatigue and wear of metalloid-ion-implanted metals

International Nuclear Information System (INIS)

Hohmuth, K.; Richter, E.; Rauschenbach, B.; Blochwitz, C.

1985-01-01

The effect of metalloid ion implantation on the fatigue behaviour and wear of nickel and two steels has been investigated. These metals were implanted with boron, carbon and nitrogen ions at energies from 30 to 60 keV and with doses from 1 X 10 16 to 1 X 10 18 ions cm -2 at room temperature. The mechanical behaviour of fatigued nickel was studied in push-pull tests at room temperature. Wear measurements were made using a pin-and-disc technique. The surface structure, dislocation arrangement and modification of the implantation profile resulting from mechanical tests on metals which had been implanted with metalloid ions were examined using high voltage electron microscopy, transmission high energy electron diffraction, scanning electron microscopy and Auger electron spectroscopy. It is reported that nitrogen and boron ion implantation improves the fatigue lifetime, changes the number and density of the slip bands and modifies the dislocation arrangements in nickel. The cyclic deformation leads to recrystallization of the boron-ion-induced amorphous structure of nickel and to diffusion of the boron and nitrogen in the direction of the surface. The wear behaviour of steels was improved by implantation of mass-separated ions and by implantation of ions without mass separation. (Auth.)

Neutralization by metal ions of the toxicity of sodium selenide.

Directory of Open Access Journals (Sweden)

Marc Dauplais

Full Text Available Inert metal-selenide colloids are found in animals. They are believed to afford cross-protection against the toxicities of both metals and selenocompounds. Here, the toxicities of metal salt and sodium selenide mixtures were systematically studied using the death rate of Saccharomyces cerevisiae cells as an indicator. In parallel, the abilities of these mixtures to produce colloids were assessed. Studied metal cations could be classified in three groups: (i metal ions that protect cells against selenium toxicity and form insoluble colloids with selenide (Ag⁺, Cd²⁺, Cu²⁺, Hg²⁺, Pb²⁺ and Zn²⁺, (ii metal ions which protect cells by producing insoluble metal-selenide complexes and by catalyzing hydrogen selenide oxidation in the presence of dioxygen (Co²⁺ and Ni²⁺ and, finally, (iii metal ions which do not afford protection and do not interact (Ca²⁺, Mg²⁺, Mn²⁺ or weakly interact (Fe²⁺ with selenide under the assayed conditions. When occurring, the insoluble complexes formed from divalent metal ions and selenide contained equimolar amounts of metal and selenium atoms. With the monovalent silver ion, the complex contained two silver atoms per selenium atom. Next, because selenides are compounds prone to oxidation, the stabilities of the above colloids were evaluated under oxidizing conditions. 5,5'-dithiobis-(2-nitrobenzoic acid (DTNB, the reduction of which can be optically followed, was used to promote selenide oxidation. Complexes with cadmium, copper, lead, mercury or silver resisted dissolution by DTNB treatment over several hours. With nickel and cobalt, partial oxidation by DTNB occurred. On the other hand, when starting from ZnSe or FeSe complexes, full decompositions were obtained within a few tens of minutes. The above properties possibly explain why ZnSe and FeSe nanoparticles were not detected in animals exposed to selenocompounds.

Metal ion binding to iron oxides

Science.gov (United States)

Ponthieu, M.; Juillot, F.; Hiemstra, T.; van Riemsdijk, W. H.; Benedetti, M. F.

2006-06-01

The biogeochemistry of trace elements (TE) is largely dependent upon their interaction with heterogeneous ligands including metal oxides and hydrous oxides of iron. The modeling of TE interactions with iron oxides has been pursued using a variety of chemical models. The objective of this work is to show that it is possible to model the adsorption of protons and TE on a crystallized oxide (i.e., goethite) and on an amorphous oxide (HFO) in an identical way. Here, we use the CD-MUSIC approach in combination with valuable and reliable surface spectroscopy information about the nature of surface complexes of the TE. The other objective of this work is to obtain generic parameters to describe the binding of the following elements (Cd, Co, Cu, Ni, Pb, and Zn) onto both iron oxides for the CD-MUSIC approach. The results show that a consistent description of proton and metal ion binding is possible for goethite and HFO with the same set of model parameters. In general a good prediction of almost all the collected experimental data sets corresponding to metal ion binding to HFO is obtained. Moreover, dominant surface species are in agreement with the recently published surface complexes derived from X-ray absorption spectroscopy (XAS) data. Until more detailed information on the structure of the two iron oxides is available, the present option seems a reasonable approximation and can be used to describe complex geochemical systems. To improve our understanding and modeling of multi-component systems we need more data obtained at much lower metal ion to iron oxide ratios in order to be able to account eventually for sites that are not always characterized in spectroscopic studies.

Effects of metal-ion replacement on pyrazinamidase activity: A quantum mechanical study.

Science.gov (United States)

Khadem-Maaref, Mahmoud; Mehrnejad, Faramarz; Phirouznia, Arash

2017-05-01

Pyrazinamidase (PZase), a metalloenzyme, is responsible for acidic modification of pyrazinamide (PZA), a drug used in tuberculosis treatment. The metal coordination site of the enzyme is able to coordinate various divalent metal cofactors. Previous experimental studies have demonstrated that metal ions, such as Co 2+ , Mn 2+ , and Zn 2+ , are able to reactivate metal-depleted PZase, while others including Cu 2+ , Fe 2+ , and Mg 2+ , cannot restore activity. In this study, we investigated binding of various metal ions to the metal coordination site (MCS) of the enzyme using quantum mechanical calculations. We calculated the metal-ligand (residue) binding energy and the atomic partial charges in the presence of various ions. The results indicated that the tendency of alkaline earth metals to bind to PZase MCS is very low and not suitable for enzyme structural and catalytic function. In contrast, Co 2+ and Ni 2+ ions have very high binding affinity and are favorable to the structural and functional properties of the enzyme. Furthermore, we observed that the rate at which Ni 2+ , Co 2+ and Fe 2+ ions in PZase MCS polarize the OH bond of coordinated water molecules is much higher than the polarization rate created by other ions. This finding suggests that the coordination of Ni 2+ , Co 2+ , or Fe 2+ to PZase facilitates the deprotonation of coordinated water molecules to generate a nucleophile that catalyzes the enzymatic reaction. Copyright © 2017 Elsevier Inc. All rights reserved.

Long range implantation by MEVVA metal ion source

International Nuclear Information System (INIS)

Zhang Tonghe; Wu Yuguang; Ma Furong; Liang Hong

2001-01-01

Metal vapor vacuum arc (MEVVA) source ion implantation is a new technology used for achieving long range ion implantation. It is very important for research and application of the ion beam modification of materials. The results show that the implanted atom diffusion coefficient increases in Mo implanted Al with high ion flux and high dose. The implanted depth is 311.6 times greater than that of the corresponding ion range. The ion species, doses and ion fluxes play an important part in the long-range implantation. Especially, thermal atom chemistry have specific effect on the long-range implantation during high ion flux implantation at transient high target temperature

Isotherms of ion exchange on titanates of alkaline metals

International Nuclear Information System (INIS)

Fillina, L.P.; Belinskaya, F.A.

1986-01-01

Present article is devoted to isotherms of ion exchange on titanates of alkaline metals. Therefore, finely dispersed hydrated titanates of alkaline metals (lithium, sodium, potassium) with ion exchange properties are obtained by means of alkaline hydrolysis of titanium chloride at high ph rates. Sorption of cations from salts solution of Li 2 SO 4 , NaNO 3 , Ca(NO 3 ) 2 , AgNO 3 by titanates is studied.

Ion irradiation effect on metallic condensate adhesion to glass

International Nuclear Information System (INIS)

Kovalenko, V.V.; Upit, G.P.

1984-01-01

The ion irradiation effect on metallic condensate adhesion to glass is investigated. It has been found that in case of indium ion deposition the condensate adhesion to glass cleavages being in contact with atmosphere grows up to the level corresponding to a juvenile surface while in case of argon ion irradiation - exceeds it. It is shown that the observed adhesion growth is determined mainly by the surfwce modification comparising charge accumulation on surface, destruction of a subsurface layer and an interlayer formation in the condensate-substrate interface. The role of these factors in the course of various metals deposition is considered

A computational study of adsorption of divalent metal ions on graphene oxide

Directory of Open Access Journals (Sweden)

Somphob Thompho

2017-12-01

Full Text Available Adsorption of divalent metal ions (Pb2+,Cd2+, Zn2+,Cu2+ on graphene oxide (GO was studied using density functional theory (DFT. Adsorption geometries and energies, as well as the nature of the binding energy, were calculated for the interaction of divalent metal ions with oxygen-containing groups on the surface of GO. The configurations of the complexes were modeled by placing the divalent metal ions above the center and perpendicular to the surface. Binding of Cu2+ to the GO sheet was predicted to be much stronger than that for other divalent metal ions. Calculated results show good agreement with experimental observations and provide useful information for environmental pollution cleanup.

Facile synthesis of Fe3O4@PDA core-shell microspheres functionalized with various metal ions: A systematic comparison of commonly-used metal ions for IMAC enrichment.

Science.gov (United States)

Jiang, Jiebing; Sun, Xueni; Li, Yan; Deng, Chunhui; Duan, Gengli

2018-02-01

Metal ions differed greatly in affinity towards phosphopeptides, and thus it is essential to systematically compare the phosphopeptides enrichment ability of different metal ions usually used in the IMAC techniques. In this work, for the first time, eight metal ions, including Nb 5+ , Ti 4+ , Zr 4+ , Ga 3+ , Y 3+ , In 3+ , Ce 4+ , Fe 3+ , were immobilized on the polydopamine (PDA)-coated Fe 3 O 4 (denoted as Fe 3 O 4 @PDA-M n+ ), and systematically compared by the real biosamples, in addition to standard phosphopeptides. Fe 3 O 4 microspheres were synthesized via the solvothermal reaction, followed by self-polymerization of dopamine on the surface. Then through taking advantage of the hydroxyl and amino group of PDA, the eight metal ions were easily adhered to the surface of Fe 3 O 4 @PDA. After characterization, the resultant Fe 3 O 4 @PDA-M n+ microspheres were applied to phosphopeptides enrichment based on the binding affinity between metal ions and phosphopeptides. According to the results, different metal ions presented diverse phosphopeptides enrichment efficiency in terms of selectivity, sensitivity and the enrichment ability from real complex samples, and Fe 3 O 4 @PDA-Nb 5+ and Fe 3 O 4 @PDA-Ti 4+ showed obvious advantages of the phosphopeptides enrichment effect after the comparison. This systematic comparison may provide certain reference for the use and development of IMAC materials in the future. Copyright © 2017 Elsevier B.V. All rights reserved.

Investigation of metal ions sorption of brown peat moss powder

Science.gov (United States)

Kelus, Nadezhda; Blokhina, Elena; Novikov, Dmitry; Novikova, Yaroslavna; Chuchalin, Vladimir

2017-11-01

For regularities research of sorptive extraction of heavy metal ions by cellulose and its derivates from aquatic solution of electrolytes it is necessary to find possible mechanism of sorption process and to choice a model describing this process. The present article investigates the regularities of aliovalent metals sorption on brown peat moss powder. The results show that sorption isotherm of Al3+ ions is described by Freundlich isotherm and sorption isotherms of Na+ i Ni2+ are described by Langmuir isotherm. To identify the mechanisms of brown peat moss powder sorption the IR-spectra of the initial brown peat moss powder samples and brown peat moss powder samples after Ni (II) sorption were studied. Metal ion binding mechanisms by brown peat moss powder points to ion exchange, physical adsorption, and complex formation with hydroxyl and carboxyl groups.

Modification of solid surface by intense pulsed light-ion and metal-ion beams

Science.gov (United States)

Nakagawa, Y.; Ariyoshi, T.; Hanjo, H.; Tsutsumi, S.; Fujii, Y.; Itami, M.; Okamoto, A.; Ogawa, S.; Hamada, T.; Fukumaru, F.

1989-03-01

Metal surfaces of Al, stainless-steel and Ti were bombarded with focused intense pulsed proton and carbon ion beams (energy ˜ 80 keV, current density ≲ 1000 A/cm 2, pulse width ˜ 300 ns). Thin titanium carbide layers were produced by carbon-ion irradiation on the titanium surface. The observed molten surface structures and recrystallized layer (20 μm depth) indicated that the surfaces reached high temperatures as a result of the irradiation. The implantation of intense pulsed metal ion beams (Al +, ˜ 20 A/cm 2) with simultaneous deposition of anode metal vapor on Ti and Fe made a mixed layer of AlTi and AlFe of about 0.5 μm depth. Ti and B multilayered films evaporated on glass substrates were irradiated by intense pulsed proton beams of relatively lower current density (10-200 A/cm 2). Ti films containing B atoms above 10 at.% were obtained. When the current density was about 200 A/cm 2 diffraction peaks of TiB 2 appeared.

Pure high dose metal ion implantation using the plasma immersion technique

International Nuclear Information System (INIS)

Zhang, T.; Tang, B.Y.; Zeng, Z.M.; Kwok, T.K.; Chu, P.K.; Monteiro, O.R.; Brown, I.G.

1999-01-01

High energy implantation of metal ions can be carried out using conventional ion implantation with a mass-selected ion beam in scanned-spot mode by employing a broad-beam approach such as with a vacuum arc ion source, or by utilizing plasma immersion ion implantation with a metal plasma. For many high dose applications, the use of plasma immersion techniques offers a high-rate process, but the formation of a surface film along with the subsurface implanted layer is sometimes a severe or even fatal detriment. We describe here an operating mode of the metal plasma immersion approach by which pure implantation can be obtained. We have demonstrated the technique by carrying out Ti and Ta implantations at energies of about 80 and 120 keV for Ti and Ta, respectively, and doses on the order of 1x10 17 ions/cm 2 . Our experiments show that virtually pure implantation without simultaneous surface deposition can be accomplished. Using proper synchronization of the metal arc and sample voltage pulse, the applied dose that deposits as a film versus the part that is energetically implanted (the deposition-to-implantation ratio) can be precisely controlled.copyright 1999 American Institute of Physics

Acetabular bone density and metal ions after metal-on-metal versus metal-on-polyethylene total hip arthroplasty; short-term results

NARCIS (Netherlands)

Zijlstra, Wierd P.; van der Veen, Hugo C.; van den Akker-Scheek, Inge; Zee, Mark J. M.; Bulstra, Sjoerd K.; van Raay, Jos J. A. M.

Information on periprosthetic acetabular bone density is lacking for metal-on-metal total hip arthroplasties. These bearings use cobalt-chromium instead of titanium acetabular components, which could lead to stress shielding and hence periprosthetic bone loss. Cobalt and chromium ions have

Selective transport and incorporation of highly charged metal and metal complex ions in self-assembled polyelectrolyte multilayer membranes

International Nuclear Information System (INIS)

Toutianoush, Ali; Tieke, Bernd

2002-01-01

The transport of aqueous salts containing mono-, di- and trivalent metal and tetravalent metal complex ions across ultrathin polyvinylammonium/polyvinylsulphate (PVA/PVS) membranes is described. The membranes were prepared by electrostatic layer-by-layer (LBL) assembly of the two polyelectrolytes. Using spectroscopic measurements and permeability studies, it is demonstrated that the transport of copper(II) chloride, lanthanum(III) chloride, barium chloride and potassium hexacyanoferrate(II) is accompanied by the permanent incorporation of the metal and metal complex ions in the membrane. Upon the uptake of copper, lanthanum and hexacyanoferrate ions, the membranes become cross-linked so that the permeation rates of other salts not taken up by the membrane, e.g. sodium chloride, potassium chloride and magnesium chloride, are decreased. The uptake of barium ions leads to a decrease of the cross-linking density of the membrane so that the permeation rate of NaCl is increased. Possible mechanisms for the ion uptake are discussed

Metals in proteins: correlation between the metal-ion type, coordination number and the amino-acid residues involved in the coordination.

Science.gov (United States)

Dokmanić, Ivan; Sikić, Mile; Tomić, Sanja

2008-03-01

Metal ions are constituents of many metalloproteins, in which they have either catalytic (metalloenzymes) or structural functions. In this work, the characteristics of various metals were studied (Cu, Zn, Mg, Mn, Fe, Co, Ni, Cd and Ca in proteins with known crystal structure) as well as the specificity of their environments. The analysis was performed on two data sets: the set of protein structures in the Protein Data Bank (PDB) determined with resolution metal ion and its electron donors and the latter was used to assess the preferred coordination numbers and common combinations of amino-acid residues in the neighbourhood of each metal. Although the metal ions considered predominantly had a valence of two, their preferred coordination number and the type of amino-acid residues that participate in the coordination differed significantly from one metal ion to the next. This study concentrates on finding the specificities of a metal-ion environment, namely the distribution of coordination numbers and the amino-acid residue types that frequently take part in coordination. Furthermore, the correlation between the coordination number and the occurrence of certain amino-acid residues (quartets and triplets) in a metal-ion coordination sphere was analysed. The results obtained are of particular value for the identification and modelling of metal-binding sites in protein structures derived by homology modelling. Knowledge of the geometry and characteristics of the metal-binding sites in metalloproteins of known function can help to more closely determine the biological activity of proteins of unknown function and to aid in design of proteins with specific affinity for certain metals.

Accelerated electron exchange between U4+ and UO22+ by foreign metal ions

International Nuclear Information System (INIS)

Obanawa, Heiichiro; Onitsuka, Hatsuki; Takeda, Kunihiko

1990-01-01

The rate constant of U 4+ -UO 2 2+ electron exchange (k et ) was increased by more than 100 times in the presence of various metal ions. The larger rate constant was observed for the smaller difference of the standard reduction potential strength between metal ion and UO 2 2+ ion (Δμ θ e ). Detailed investigation of the electron exchange reaction in the presence of Mo 5+ suggested that the mechanism of the electron transfer reaction catalyzed by metal ions is the outer-sphere type independent of U-Clcomplex ions. (author)

Removal and recovery of toxic metal ions from aqueous waste sites using polymer pendant ligands

International Nuclear Information System (INIS)

Fish, D.

1996-01-01

The purpose of this project is to investigate the use of polymer pendant ligand technology to remove and recover toxic metal ions from DOE aqueous waste sites. Polymer pendant lgiands are organic ligands, anchored to crosslinked, modified divinylbenzene-polystyrene beads, that can selectively complex metal ions. The metal ion removal step usually occurs through a complexation or ion exchange phenomena, thus recovery of the metal ions and reuse of the beads is readily accomplished

Some aspects of metallic ion chemistry and dynamics in the mesosphere and thermosphere

Science.gov (United States)

Mathews, J. D.

1987-01-01

The relationship between the formation of sporadic layers of metallic ion and the dumping of these ions into the upper mesosphere is discussed in terms of the tidal wind, classical (i.e., windshear) and other more complex, perhaps highly nonlinear layer formation mechanisms, and a possible circulation mechanism for these ions. Optical, incoherent scatter radar, rocket, and satellite derived evidence for various layer formation mechanisms and for the metallic ion circulation system is reviewed. The results of simple one dimensional numerical model calculations of sporadic E and intermediate layer formation are presented along with suggestions for more advanced models of intense or blanketing sporadic E. The flux of metallic ions dumped by the tidal wind system into the mesosphere is estimated and compared with estimates of total particle flux of meteoric origin. Possible effects of the metallic ion flux and of meteoric dust on D region ion chemistry are discussed.

Ranges of ions in metals for use in particle treatment planning

International Nuclear Information System (INIS)

Jaekel, Oliver

2006-01-01

In proton and ion radiotherapy, the range of particles is calculated from x-ray computed tomography (CT) numbers. Due to the strong absorption of x-rays in a metal and a cut-off for large Hounsfield units (HU) in the software of most CT-scanners, a range calculation in metals cannot be based on the measured HU. This is of special importance when metal implants such as gold fillings or hip prostheses are close to the treatment volume. In order to overcome this problem in treatment planning for heavy charged particles, the correct ranges of ions in the metal relative to water have to be assigned in the CT data. Measurements and calculations of carbon ion ranges in various metals are presented that can be used in treatment planning to allow for a more accurate range calculation of carbon ion beams in titanium, steel, tungsten and gold. The suggested values for the relative water-equivalent range and their uncertainties are 3.13 (±3%) for titanium, 5.59 (±3%) for stainless steel and 10.25 (±4%) for gold. (note)

Sensing of heavy metal ions by intrinsic TMV coat protein fluorescence

Science.gov (United States)

Bayram, Serene S.; Green, Philippe; Blum, Amy Szuchmacher

2018-04-01

We propose the use of a cysteine mutant of TMV coat protein as a signal transducer for the selective sensing and quantification of the heavy metal ions, Cd2+, Pb2+, Zn2+ and Ni2+ based on intrinsic tryptophan quenching. TMV coat protein is inexpensive, can be mass-produced since it is expressed and extracted from E-coli. It also displays several different functional groups, enabling a wide repertoire of bioconjugation chemistries; thus it can be easily integrated into functional devices. In addition, TMV-ion interactions have been widely reported and utilized for metallization to generate organic-inorganic hybrid composite novel materials. Building on these previous observations, we herein determine, for the first time, the TMV-ion binding constants assuming the static fluorescence quenching model. We also show that by comparing TMV-ion interactions between native and denatured coat protein, we can distinguish between chemically similar heavy metal ions such as cadmium and zinc ions.

Smart responsive microcapsules capable of recognizing heavy metal ions.

Science.gov (United States)

Pi, Shuo-Wei; Ju, Xiao-Jie; Wu, Han-Guang; Xie, Rui; Chu, Liang-Yin

2010-09-15

Smart responsive microcapsules capable of recognizing heavy metal ions are successfully prepared with oil-in-water-in-oil double emulsions as templates for polymerization in this study. The microcapsules are featured with thin poly(N-isopropylacrylamide-co-benzo-18-crown-6-acrylamide) (P(NIPAM-co-BCAm)) membranes, and they can selectively recognize special heavy metal ions such as barium(II) or lead(II) ions very well due to the "host-guest" complexation between the BCAm receptors and barium(II) or lead(II) ions. The stable BCAm/Ba(2+) or BCAm/Pb(2+) complexes in the P(NIPAM-co-BCAm) membrane cause a positive shift of the volume phase transition temperature of the crosslinked P(NIPAM-co-BCAm) hydrogel to a higher temperature, and the repulsion among the charged BCAm/Ba(2+) or BCAm/Pb(2+) complexes and the osmotic pressure within the P(NIPAM-co-BCAm) membranes result in the swelling of microcapsules. Induced by recognizing barium(II) or lead(II) ions, the prepared microcapsules with P(NIPAM-co-BCAm) membranes exhibit isothermal and significant swelling not only in outer and inner diameters but also in the membrane thickness. The proposed microcapsules in this study are highly attractive for developing smart sensors and/or carriers for detection and/or elimination of heavy metal ions. Copyright 2010 Elsevier Inc. All rights reserved.

Ion Transport and Structure in Polymer Electrolytes with Applications in Lithium Batteries

Science.gov (United States)

Chintapalli, Mahati

When mixed with lithium salts, polymers that contain more than one chemical group, such as block copolymers and endgroup-functionalized polymers, are promising electrolyte materials for next-generation lithium batteries. One chemical group can provide good ion solvation and transport properties, while the other chemical group can provide secondary properties that improve the performance characteristics of the battery. Secondary properties of interest include non-flammability for safer lithium ion batteries and high mechanical modulus for dendrite resistance in high energy density lithium metal batteries. Block copolymers and other materials with multiple chemical groups tend to exhibit nanoscale heterogeneity and can undergo microphase separation, which impacts the ion transport properties. In block copolymers that microphase separate, ordered self-assembled structures occur on longer length scales. Understanding the interplay between structure at different length scales, salt concentration, and ion transport is important for improving the performance of multifunctional polymer electrolytes. In this dissertation, two electrolyte materials are characterized: mixtures of endgroup-functionalized, short chain perfluoropolyethers (PFPEs) and lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) salt, and mixtures of polystyrene-block-poly(ethylene oxide) (PS- b-PEO; SEO) and LiTFSI. The PFPE/LiTFSI electrolytes are liquids in which the PFPE backbone provides non-flammability, and the endgroups resemble small molecules that solvate ions. In these electrolytes, the ion transport properties and nanoscale heterogeneity (length scale 1 nm) are characterized as a function of endgroup using electrochemical techniques, nuclear magnetic resonance spectroscopy, and wide angle X-ray scattering. Endgroups, especially those containing PEO segments, have a large impact on ionic conductivity, in part because the salt distribution is not homogenous; we find that salt partitions

MTS-MD of Biomolecules Steered with 3D-RISM-KH Mean Solvation Forces Accelerated with Generalized Solvation Force Extrapolation.

Science.gov (United States)

Omelyan, Igor; Kovalenko, Andriy

2015-04-14

We developed a generalized solvation force extrapolation (GSFE) approach to speed up multiple time step molecular dynamics (MTS-MD) of biomolecules steered with mean solvation forces obtained from the 3D-RISM-KH molecular theory of solvation (three-dimensional reference interaction site model with the Kovalenko-Hirata closure). GSFE is based on a set of techniques including the non-Eckart-like transformation of coordinate space separately for each solute atom, extension of the force-coordinate pair basis set followed by selection of the best subset, balancing the normal equations by modified least-squares minimization of deviations, and incremental increase of outer time step in motion integration. Mean solvation forces acting on the biomolecule atoms in conformations at successive inner time steps are extrapolated using a relatively small number of best (closest) solute atomic coordinates and corresponding mean solvation forces obtained at previous outer time steps by converging the 3D-RISM-KH integral equations. The MTS-MD evolution steered with GSFE of 3D-RISM-KH mean solvation forces is efficiently stabilized with our optimized isokinetic Nosé-Hoover chain (OIN) thermostat. We validated the hybrid MTS-MD/OIN/GSFE/3D-RISM-KH integrator on solvated organic and biomolecules of different stiffness and complexity: asphaltene dimer in toluene solvent, hydrated alanine dipeptide, miniprotein 1L2Y, and protein G. The GSFE accuracy and the OIN efficiency allowed us to enlarge outer time steps up to huge values of 1-4 ps while accurately reproducing conformational properties. Quasidynamics steered with 3D-RISM-KH mean solvation forces achieves time scale compression of conformational changes coupled with solvent exchange, resulting in further significant acceleration of protein conformational sampling with respect to real time dynamics. Overall, this provided a 50- to 1000-fold effective speedup of conformational sampling for these systems, compared to conventional MD

The chemistry of the liquid alkali metals

International Nuclear Information System (INIS)

Addison, C.C.

1984-01-01

A study of liquid alkali metals. It encourages comparison with molecular solvents in chapter covering the nature and reactivity of dissolved species, solvation, solubility and electrical conductivity of solutions. It demonstrates lab techniques unique to liquid alkali metals. It discusses large-scale applications from storage batteries to sodium-cooled reactors and future fusion reactors, and associated technological problems. Contents: Some Basic Physical and Chemical Properties; Manipulation of the Liquids; The Chemistry of Purification Methods; Species Formed by Dissolved Elements; Solubilities and Analytical Methods; Alkali Metal Mixtures; Solvation in Liquid Metal; Reactions Between Liquid Alkali Metals and Water; Reactions of Nitrogen with Lithium and the Group II Metals in Liquid Sodium; The Formation, Dissociation and Stability of Heteronuclear Polyatomic Anions; Reactions of the Liquid Alkali Metals and Their Alloys with Simple Alipatic Hydrocarbons; Reactions of the Liquid Alkali Metals with Some Halogen Compounds; Hydrogen, Oxygen and Carbon Meters; Surface Chemistry and Wetting; Corrosion of Transition Metals by the Liquid Alkali Metals; Modern Applications of the Liquid Alkali Metals

Solvent effects on ion-receptor interactions in the presence of an external electric field.

Science.gov (United States)

Novák, Martin; Foroutan-Nejad, Cina; Marek, Radek

2016-11-09

In this work we investigated the influence of an external electric field on the arrangement of the solvent shells around ions interacting with a carbon-based receptor. Our survey reveals that the mechanism of interaction between a monoatomic ion and a π-type ion receptor varies by the variation in the solvent polarity, the nature of the ion, and the strength of the external field. The characteristics of the ion-surface interaction in nonpolar solvents are similar to those observed in a vacuum. However, in water, we identified two mechanisms. Soft and polarizable ions preferentially interact with the π-receptor. In contrast, two bonded states were found for hard ions. A fully solvated ion, weakly interacting with the receptor at weak field, and a strong π-complex at the strong-field regime were identified. An abrupt variation in the potential energy surface (PES) associated with the rearrangement of the solvation shell on the surface of the receptor induced by an external field was observed both in implicit and explicit solvent environments. The electric field at which the solvation shell breaks is proportional to the hardness of the ion as has been suggested recently based on experimental observations.

Do soft drinks affect metal ions release from orthodontic appliances?

Science.gov (United States)

Mikulewicz, Marcin; Wołowiec, Paulina; Loster, Bartłomiej W; Chojnacka, Katarzyna

2015-01-01

The effect of orange juice and Coca Cola(®) on the release of metal ions from fixed orthodontic appliances. A continuous flow system designed for in vitro testing of orthodontic appliances was used. Orange juice/Coca Cola(®) was flowing through the system alternately with artificial saliva for 5.5 and 18.5h, respectively. The collected samples underwent a multielemental ICP-OES analysis in order to determine the metal ions release pattern in time. The total mass of ions released from the appliance into orange juice and Coca Cola(®) (respectively) during the experiment was calculated (μg): Ni (15.33; 37.75), Cr (3.604; 1.052), Fe (48.42; ≥ 156.1), Cu (57.87, 32.91), Mn (9.164; 41.16), Mo (9.999; 30.12), and Cd (0.5967; 2.173). It was found that orange juice did not intensify the release of metal ions from orthodontic appliances, whereas Coca Cola(®) caused increased release of Ni ions. Copyright © 2015 Elsevier GmbH. All rights reserved.

Metallization of ion beam synthesized Si/3C-SiC/Si layer systems by high-dose implantation of transition metal ions

International Nuclear Information System (INIS)

Lindner, J.K.N.; Wenzel, S.; Stritzker, B.

2001-01-01

The formation of metal silicide layers contacting an ion beam synthesized buried 3C-SiC layer in silicon by means of high-dose titanium and molybdenum implantations is reported. Two different strategies to form such contact layers are explored. The titanium implantation aims to convert the Si top layer of an epitaxial Si/SiC/Si layer sequence into TiSi 2 , while Mo implantations were performed directly into the SiC layer after selectively etching off all capping layers. Textured and high-temperature stable C54-TiSi 2 layers with small additions of more metal-rich silicides are obtained in the case of the Ti implantations. Mo implantations result in the formation of the high-temperature phase β-MoSi 2 , which also grows textured on the substrate. The formation of cavities in the silicon substrate at the lower SiC/Si interface due to the Si consumption by the growing silicide phase is observed in both cases. It probably constitutes a problem, occurring whenever thin SiC films on silicon have to be contacted by silicide forming metals independent of the deposition technique used. It is shown that this problem can be solved with ion beam synthesized contact layers by proper adjustment of the metal ion dose

Effects of metal ions on the catalytic degradation of dicofol by cellulase.

Science.gov (United States)

Zhai, Zihan; Yang, Ting; Zhang, Boya; Zhang, Jianbo

2015-07-01

A new technique whereby cellulase immobilized on aminated silica was applied to catalyze the degradation of dicofol, an organochlorine pesticide. In order to evaluate the performance of free and immobilized cellulase, experiments were carried out to measure the degradation efficiency. The Michaelis constant, Km, of the reaction catalyzed by immobilized cellulase was 9.16 mg/L, and the maximum reaction rate, Vmax, was 0.40 mg/L/min, while that of free cellulase was Km=8.18 mg/L, and Vmax=0.79 mg/L/min, respectively. The kinetic constants of catalytic degradation were calculated to estimate substrate affinity. Considering that metal ions may affect enzyme activity, the effects of different metal ions on the catalytic degradation efficiency were explored. The results showed that the substrate affinity decreased after immobilization. Monovalent metal ions had no effect on the reaction, while divalent metal ions had either positive or inhibitory effects, including activation by Mn2+, reversible competition with Cd2+, and irreversible inhibition by Pb2+. Ca2+ promoted the catalytic degradation of dicofol at low concentrations, but inhibited it at high concentrations. Compared with free cellulase, immobilized cellulase was affected less by metal ions. This work provided a basis for further studies on the co-occurrence of endocrine-disrupting chemicals and heavy metal ions in the environment. Copyright © 2015. Published by Elsevier B.V.

Application of Sargassum biomass to remove heavy metal ions from synthetic multi-metal solutions and urban storm water runoff.

Science.gov (United States)

Vijayaraghavan, K; Teo, Ting Ting; Balasubramanian, R; Joshi, Umid Man

2009-05-30

The ability of Sargassum sp. to biosorb four metal ions, namely lead, copper, zinc, and manganese from a synthetic multi-solute system and real storm water runoff has been investigated for the first time. Experiments on synthetic multi-solute systems revealed that Sargassum performed well in the biosorption of all four metal ions, with preference towards Pb, followed by Cu, Zn, and Mn. The solution pH strongly affected the metal biosorption, with pH 6 being identified as the optimal condition for achieving maximum biosorption. Experiments at different biosorbent dosages revealed that good biosorption capacity as well as high metal removal efficiency was observed at 3g/L. The biosorption kinetics was found to be fast with equilibrium being attained within 50 min. According to the Langmuir isotherm model, Sargassum exhibited maximum uptakes of 214, 67.5, 24.2 and 20.2mg/g for lead, copper, zinc, and manganese, respectively in single-solute systems. In multi-metal systems, strong competition between four metal ions in terms of occupancy binding sites was observed, and Sargassum showed preference in the order of Pb>Cu>Zn>Mn. The application of Sargassum to remove four heavy metal ions in real storm water runoff revealed that the biomass was capable of removing the heavy metal ions. However, the biosorption performance was slightly lower compared to that of synthetic metal solutions. Several factors were responsible for this difference, and the most important factor is the presence of other contaminants such as anions, organics, and other trace metals in the runoff.

Ion-induced electron emission from clean metals

International Nuclear Information System (INIS)

Baragiola, R.A.; Alonso, E.V.; Ferron, J.; Oliva-Florio, A.; Universidad Nacional de Cuyo, San Carlos de Bariloche

1979-01-01

We report recent experimental work on electron emission from clean polycrystalline metal surfaces under ion bombardment. We critically discuss existing theories and point out the presently unsolved problems. (orig.)

Ionic liquids used in extraction and separation of metal ions

International Nuclear Information System (INIS)

Shen Xinghai; Xu Chao; Liu Xinqi; Chu Taiwei

2006-01-01

Ionic liquids as green solvents now have become a research hotspot in the field of separation of metal ions by solvent extraction. Experimental results of extraction of various metal ions with ionic liquids as solvents, including that of alkali metals, alkaline earths, transition metals rare earths and actinides are introduced. The extraction of uranium, plutonium and fission products that are involved in spent nuclear fuel reprocessing is also reviewed. The possible extraction mechanisms are discussed. Finally, the prospect of replacement of volatile and/or toxic organic solvents with environmentally benign ionic liquids for solvent extraction and the potency of applications of ionic liquids in solvent extraction are also commented. (authors)

Cleavage reactions of the complex ions derived from self-complementary deoxydinucleotides and alkali-metal ions using positive ion electrospray ionization with tandem mass spectrometry.

Science.gov (United States)

Xiang, Yun; Abliz, Zeper; Takayama, Mitsuo

2004-05-01

The dissociation reactions of the adduct ions derived from the four self-complementary deoxydinucleotides, d(ApT), d(TpA), d(CpG), d(GpC), and alkali-metal ions were studied in detail by positive ion electrospray ionization multiple-stage mass spectrometry (ESI-MS(n)). For the [M + H](+) ions of the four deoxydinucleotides, elimination of 5'-terminus base or loss of both of 5'-terminus base and a deoxyribose were the major dissociation pathway. The ESI-MS(n) spectra showed that Li(+), Na(+), and Cs(+) bind to deoxydinucleotides mainly by substituting the H(+) of phosphate group, and these alkali-metal ions preferred to bind to pyrimidine bases rather than purine bases. For a given deoxydinucleotide, the dissociation pathway of [M + K](+) ions differed clearly from that of [M + Li](+), [M + Na](+), and [M + Cs](+) ions. Some interesting and characteristic cleavage reactions were observed in the product-ion spectra of [M + K](+) ions, including direct elimination of deoxyribose and HPO(3) from molecular ions. The fragmentation behavior of the [M + K](+) and [M + W](+) (W = Li, Na, Cs) adduct ions depend upon the sequence of bases, the interaction between alkali-metal ions and nucleobases, and the steric hindrance caused by bases.

Damage induced by helium ion irradiation in Fe-based metallic glass

Energy Technology Data Exchange (ETDEWEB)

Zhang, Xiaonan; Mei, Xianxiu, E-mail: xxmei@dlut.edu.cn; Zhang, Qi; Li, Xiaona; Qiang, Jianbing; Wang, Younian

2017-07-15

The changes in structure and surface morphology of metallic glasses Fe{sub 80}Si{sub 7.43}B{sub 12.57} and Fe{sub 68}Zr{sub 7}B{sub 25} before and after the irradiation of He ions with the energy of 300 keV were investigated, and were compared with that of the tungsten. The results show that after the He{sup 2+} irradiation, metallic glass Fe{sub 68}Zr{sub 7}B{sub 25} still maintained amorphous. While a small amount of metastable β-Mn type phase nanocrystals formed in metallic glass Fe{sub 80}Si{sub 7.43}B{sub 12.57} at the fluence of 4.0 × 10{sup 17}ions/cm{sup 2} (19dpa). The nanocrystals transformed into α-Fe phase and tetragonal Fe{sub 2}B phase as the fluence increased to 1.0 × 10{sup 18}ions/cm{sup 2} (47dpa). Then the new orthogonal Fe{sub 3}B phase and β-Mn type phase nanocrystals appeared when the fluence increased further, and the quantities of nanocrystals increased. Blisters and cracks appeared on the surface of tungsten under the irradiation fluence of 1.0 × 10{sup 18}ions/cm{sup 2}, however only when the fluence was up to 1.6 × 10{sup 18}ions/cm{sup 2}, could cracks and spalling appear on the surfaces of metallic glasses. - Highlights: •Metallic glass Fe{sub 68}Zr{sub 7}B{sub 25} could maintain amorphous state after the irradiation. •A series of crystallization behaviors occurred in metallic glass Fe{sub 80}Si{sub 7.43}B{sub 12.57}. •The surface of tungsten appeared blisters at the fluence of 1.0 × 10{sup 18} ions/cm{sup 2}. •Surfaces of Fe-based metallic glasses cracked at the fluence of 1.6 × 10{sup 18}ions/cm{sup 2}.

The fabrication of metal silicide nanodot arrays using localized ion implantation

International Nuclear Information System (INIS)

Han, Jin; Kim, Tae-Gon; Min, Byung-Kwon; Lee, Sang Jo

2010-01-01

We propose a process for fabricating nanodot arrays with a pitch size of less than 25 nm. The process consists of localized ion implantation in a metal thin film on a Si wafer using a focused ion beam (FIB), followed by chemical etching. This process utilizes the etching resistivity changes of the ion beam irradiated region that result from metal silicide formation by ion implantation. To control the nanodot diameter, a threshold ion dose model is proposed using the Gaussian distribution of the ion beam intensities. The process is verified by fabricating nanodots with various diameters. The mechanism of etching resistivity is investigated via x-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES).

A high current metal vapour vacuum arc ion source for ion implantation studies

International Nuclear Information System (INIS)

Evans, P.J.; Noorman, J.T.; Watt, G.C.; Cohen, D.D.; Bailey, G.M.

1989-01-01

The main features of the metal vapour vacuum arc(MEVA) as an ion source are presented. The technology utilizes the plasma production capabilities of a vacuum arc cathode. Some of the ions produced in this discharge flow through the anode and the 3 extraction grids to form an extracted ion beam. The high beam current and the potential for generating broad beams, make this technology suitable for implantation of large surface areas. The composition of the vacuum arc cathode determines the particular ions obtained from the MEVA source. 3 refs., 1 tab., 2 figs

The sorption of metal ions on nanoscale zero-valent iron

Directory of Open Access Journals (Sweden)

Suponik Tomasz

2017-01-01

Full Text Available The injection of the colloidal suspensions of nano-iron (nZVI into an aquifer is a novel method of removing metal ions from acidic water. In the batch tests, the equilibrium study of the sorption of metal ions, Cu(II and Zn(II, on Green Tea nanoscale Zero-Valent Ion (GT-nZVI was carried out. The sorption of metal ions on this reactive material was described using the Langmuir, Freundlich and Sips models. This last model described in a better way the sorption equilibrium in the tested range of concentrations and temperature. The value of determination coefficient (R2 for the Sips model, for copper and zinc, was 0.9735 to 0.9995, respectively. GT-nZVI has very good properties in removing Cu(II and Zn(II from acidic water. The high values of qmaxS, the maximum adsorption capacity in the Sips model, amounting to 348.0 and 267.3 mg/g for Cu(II and Zn(II, indicate the high adsorption capacity of GT-nZVI. The analyzed metals have good or very good affinity with GT-nZVI.

Polymer-supported reagents with enhanced metal ion recognition: Application to separations science

International Nuclear Information System (INIS)

Alexandratos, S.D.

1993-01-01

The design and development of polymer-supported reagents with ever-increasing specificities for targeted metal ions remains an important areas of research. The need for efficient separation schemes for both ions and molecules has been outlined in a report by the National Research Council (King) and will gain increased emphasis as environmental restoration is pursued. Polymer-supported reagents are unique in their ability to be applied in an environmentally benign manner to a host of challenges. Such reagents, in the form of beads, can be applied to continuous separation processes ranging from the removal of metal ions in water to the recovery of medicinal drugs produced through biotechnological means. The application of polymer-supported reagents to metal ion separations still requires developing a fundamental understanding of ligand-metal interactions, the role of the polymer in those interactions, and the methods of synthesizing such polymeric reagents in a readily applicable form. Ion exchange resins with sulfonic acid ligands are the prototypical polymer-supported reagents, and their properties have been exhaustively studied (Helfferich). The high acidity of the sulfonic acid group, however, precludes much selectivity, and it displays a very limited range of reaction free energy values with different metal ions (Boyd et al.). The carboxylic acid ligand, present in the acrylate resins, is more selective, though its weak acidity requires relatively high pH solutions for it to be effective. Research has thus been focused on the preparation of polymer-supported reagents with high levels of specificity for targeted metal ions

Nanodiamonds act as Trojan horse for intracellular delivery of metal ions to trigger cytotoxicity.

Science.gov (United States)

Zhu, Ying; Zhang, Yu; Shi, Guosheng; Yang, Jinrong; Zhang, Jichao; Li, Wenxin; Li, Aiguo; Tai, Renzhong; Fang, Haiping; Fan, Chunhai; Huang, Qing

2015-02-05

Nanomaterials hold great promise for applications in the delivery of various molecules with poor cell penetration, yet its potential for delivery of metal ions is rarely considered. Particularly, there is limited insight about the cytotoxicity triggered by nanoparticle-ion interactions. Oxidative stress is one of the major toxicological mechanisms for nanomaterials, and we propose that it may also contribute to nanoparticle-ion complexes induced cytotoxicity. To explore the potential of nanodiamonds (NDs) as vehicles for metal ion delivery, we used a broad range of experimental techniques that aimed at getting a comprehensive assessment of cell responses after exposure of NDs, metal ions, or ND-ion mixture: 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay, Trypan blue exclusion text, optical microscope observation, synchrotron-based scanning transmission X-ray microscopy (STXM) and micro X-ray fluorescence (μXRF) microscopy, inductively coupled plasma-mass spectrometry (ICP-MS), reactive oxygen species (ROS) assay and transmission electron microscopy (TEM) observation. In addition, theoretical calculation and molecular dynamics (MD) computation were used to illustrate the adsorption properties of different metal ion on NDs as well as release profile of ion from ND-ion complexes at different pH values. The adsorption capacity of NDs for different metal ions was different, and the adsorption for Cu2+ was the most strong among divalent metal ions. These different ND-ion complexes then had different cytotoxicity by influencing the subsequent cellular responses. Detailed investigation of ND-Cu2+ interaction showed that the amount of released Cu2+ from ND-Cu2+ complexes at acidic lysosomal conditions was much higher than that at neutral conditions, leading to the elevation of intracellular ROS level, which triggered cytotoxicity. By theoretical approaches, we demonstrated that the functional carbon surface and cluster structures of NDs made them

Poultry litter-based activated carbon for removing heavy metal ions in water.

Science.gov (United States)

Guo, Mingxin; Qiu, Guannan; Song, Weiping

2010-02-01

Utilization of poultry litter as a precursor material to manufacture activated carbon for treating heavy metal-contaminated water is a value-added strategy for recycling the organic waste. Batch adsorption experiments were conducted to investigate kinetics, isotherms, and capacity of poultry litter-based activated carbon for removing heavy metal ions in water. It was revealed that poultry litter-based activated carbon possessed significantly higher adsorption affinity and capacity for heavy metals than commercial activated carbons derived from bituminous coal and coconut shell. Adsorption of metal ions onto poultry litter-based carbon was rapid and followed Sigmoidal Chapman patterns as a function of contact time. Adsorption isotherms could be described by different models such as Langmuir and Freundlich equations, depending on the metal species and the coexistence of other metal ions. Potentially 404 mmol of Cu2+, 945 mmol of Pb2+, 236 mmol of Zn2+, and 250-300 mmol of Cd2+ would be adsorbed per kg of poultry litter-derived activated carbon. Releases of nutrients and metal ions from litter-derived carbon did not pose secondary water contamination risks. The study suggests that poultry litter can be utilized as a precursor material for economically manufacturing granular activated carbon that is to be used in wastewater treatment for removing heavy metals.

Interaction of antihypertensive drug amiloride with metal ions in micellar medium using fluorescence spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Gujar, Varsha; Pundge, Vijaykumar; Ottoor, Divya, E-mail: divya@chem.unipune.ac.in

2015-05-15

Steady state and life time fluorescence spectroscopy have been employed to study the interaction of antihypertensive drug amiloride with biologically important metal ions i.e. Cu{sup 2+}, Fe{sup 2+}, Ni{sup 2+} and Zn{sup 2+} in various micellar media (anionic SDS (sodium dodecyl sulfate), nonionic TX-100 (triton X-100) and cationic CTAB (cetyl trimethyl ammonium bromide)). It was observed that fluorescence properties of drug remain unaltered in the absence of micellar media with increasing concentration of metal ions. However, addition of Cu{sup 2+}, Fe{sup 2+} and Ni{sup 2+} caused fluorescence quenching of amiloride in the presence of anionic micelle, SDS. Binding of drug with metal ions at the charged micellar interface could be the possible reason for this pH-dependent metal-mediated fluorescence quenching. There were no remarkable changes observed due to metal ions addition when drug was present in cationic and nonionic micellar medium. The binding constant and bimolecular quenching constant were evaluated and compared for the drug–metal complexes using Stern–Volmer equation and fluorescence lifetime values. - Highlights: • Interaction of amiloride with biologically important metal ions, Fe{sup 2+}, Cu{sup 2+}, Ni{sup 2+} and Zn{sup 2+}. • Monitoring the interaction in various micelle at different pH by fluorescence spectroscopy. • Micelles acts as receptor, amiloride as transducer and metal ions as analyte in the present system. • Interaction study provides pH dependent quenching and binding mechanism of drug with metal ions.

Interaction of antihypertensive drug amiloride with metal ions in micellar medium using fluorescence spectroscopy

International Nuclear Information System (INIS)

Gujar, Varsha; Pundge, Vijaykumar; Ottoor, Divya

2015-01-01

Steady state and life time fluorescence spectroscopy have been employed to study the interaction of antihypertensive drug amiloride with biologically important metal ions i.e. Cu 2+ , Fe 2+ , Ni 2+ and Zn 2+ in various micellar media (anionic SDS (sodium dodecyl sulfate), nonionic TX-100 (triton X-100) and cationic CTAB (cetyl trimethyl ammonium bromide)). It was observed that fluorescence properties of drug remain unaltered in the absence of micellar media with increasing concentration of metal ions. However, addition of Cu 2+ , Fe 2+ and Ni 2+ caused fluorescence quenching of amiloride in the presence of anionic micelle, SDS. Binding of drug with metal ions at the charged micellar interface could be the possible reason for this pH-dependent metal-mediated fluorescence quenching. There were no remarkable changes observed due to metal ions addition when drug was present in cationic and nonionic micellar medium. The binding constant and bimolecular quenching constant were evaluated and compared for the drug–metal complexes using Stern–Volmer equation and fluorescence lifetime values. - Highlights: • Interaction of amiloride with biologically important metal ions, Fe 2+ , Cu 2+ , Ni 2+ and Zn 2+ . • Monitoring the interaction in various micelle at different pH by fluorescence spectroscopy. • Micelles acts as receptor, amiloride as transducer and metal ions as analyte in the present system. • Interaction study provides pH dependent quenching and binding mechanism of drug with metal ions

Effect of metal ions on the growth and metabolites production of ...

African Journals Online (AJOL)

Effect of metal ions on the growth and metabolites production of Ganoderma lucidum in submerged culture. YH Cui, KC Zhang. Abstract. The effects of several metal ions on the cell growth, production of polysaccharides by Ganoderma lucidum in submerged fermentation were studied. The results showed that 50 ppm Se2+ ...

Solvated protein–DNA docking using HADDOCK

International Nuclear Information System (INIS)

Dijk, Marc van; Visscher, Koen M.; Kastritis, Panagiotis L.; Bonvin, Alexandre M. J. J.

2013-01-01

Interfacial water molecules play an important role in many aspects of protein–DNA specificity and recognition. Yet they have been mostly neglected in the computational modeling of these complexes. We present here a solvated docking protocol that allows explicit inclusion of water molecules in the docking of protein–DNA complexes and demonstrate its feasibility on a benchmark of 30 high-resolution protein–DNA complexes containing crystallographically-determined water molecules at their interfaces. Our protocol is capable of reproducing the solvation pattern at the interface and recovers hydrogen-bonded water-mediated contacts in many of the benchmark cases. Solvated docking leads to an overall improvement in the quality of the generated protein–DNA models for cases with limited conformational change of the partners upon complex formation. The applicability of this approach is demonstrated on real cases by docking a representative set of 6 complexes using unbound protein coordinates, model-built DNA and knowledge-based restraints. As HADDOCK supports the inclusion of a variety of NMR restraints, solvated docking is also applicable for NMR-based structure calculations of protein–DNA complexes.

Solvated protein-DNA docking using HADDOCK

Energy Technology Data Exchange (ETDEWEB)

Dijk, Marc van; Visscher, Koen M.; Kastritis, Panagiotis L.; Bonvin, Alexandre M. J. J., E-mail: a.m.j.j.bonvin@uu.nl [Utrecht University, Bijvoet Center for Biomolecular Research, Faculty of Science-Chemistry (Netherlands)

2013-05-15

Interfacial water molecules play an important role in many aspects of protein-DNA specificity and recognition. Yet they have been mostly neglected in the computational modeling of these complexes. We present here a solvated docking protocol that allows explicit inclusion of water molecules in the docking of protein-DNA complexes and demonstrate its feasibility on a benchmark of 30 high-resolution protein-DNA complexes containing crystallographically-determined water molecules at their interfaces. Our protocol is capable of reproducing the solvation pattern at the interface and recovers hydrogen-bonded water-mediated contacts in many of the benchmark cases. Solvated docking leads to an overall improvement in the quality of the generated protein-DNA models for cases with limited conformational change of the partners upon complex formation. The applicability of this approach is demonstrated on real cases by docking a representative set of 6 complexes using unbound protein coordinates, model-built DNA and knowledge-based restraints. As HADDOCK supports the inclusion of a variety of NMR restraints, solvated docking is also applicable for NMR-based structure calculations of protein-DNA complexes.

Poisoning of liquid membrane carriers in extraction of metal ions

International Nuclear Information System (INIS)

Wang, Yuchun; Wang, Dexian

1992-01-01

As means of effective separation and preconcentration, emulsion liquid membranes (ELMs) have found application in many fields including biochemical separation, wastewater treatment, hydrometallurgy, and preconcentration in analytical chemistry. In the extraction of desired metal (scandium, mixed rare earths) ions using chelating extractants (TTA, HDEHP) as liquid membrane carriers, the carriers will become poisoned owing to the presence of even minute quantity of certain high ionic potential ions in the feed solution. The reason for the poisoning of carriers is that those ions have so much greater affinity than the desired ions for the membrane carrier that the ion-carrier coordination compound cannot be stripped at the interior interface of the membrane and gradually no more free carrier transports any metal ions across the membrane. The calculated results are in agreement with the experiments, and methods to avoid the poisoning are given in the paper

Molten salt oxidation of ion-exchange resins doped with toxic metals and radioactive metal surrogates

International Nuclear Information System (INIS)

Yang, Hee-Chul; Cho, Yong-Jun; Yoo, Jae-Hyung; Kim, Joon-Hyung; Eun, Hee-Chul

2005-01-01

Ion-exchange resins doped with toxic metals and radioactive metal surrogates were test-burned in a bench-scale molten salt oxidation (MSO) reactor system. The purposes of this study are to confirm the destruction performance of the two-stage MSO reactor system for the organic ion-exchange resin and to obtain an understanding of the behavior of the fixed toxic metals and the sulfur in the cationic exchange resins. The destruction of the organics is very efficient in the primary reactor. The primarily destroyed products such as carbon monoxide are completely oxidized in the secondary MSO reactor. The overall collection of the sulfur and metals in the two-stage MSO reactor system appeared to be very efficient. Over 99.5% of all the fixed toxic metals (lead and cadmium) and radioactive metal surrogates (cesium, cobalt, strontium) remained in the MSO reactor bottom. Thermodynamic equilibrium calculations and the XRD patterns of the spent salt samples revealed that the collected metals existed in the form of each of their carbonates or oxides, which are non-volatile species at the MSO system operating conditions. (author)

Synthesis, Characterizations, and Applications of Metal-Ions Incorporated High Quality MCM-41 Catalysts

International Nuclear Information System (INIS)

Lim, Steven S.; Haller, Gary L.

2013-01-01

Various metal ions (transition and base metals) incorporated MCM-41 catalysts can be synthesized using colloidal and soluble silica with non-sodium involved process. Transition metal ion-typically V 5+ , Co 2+ , and Ni 2+ -incorporated MCM-41 catalysts were synthesized by isomorphous substitution of Si ions in the framework. Each incorporated metal ion created a single species in the silica framework, single-site solid catalyst, showing a substantial stability in reduction and catalytic activity. Radius of pore curvature effect was investigated with Co-MCM-41 by temperature programmed reduction (TPR). The size of metallic Co clusters, sub-nanometer, could be controlled by a proper reduction treatment of Co-MCM-41 having different pore size and the initial pH adjustment of the Co-MCM-41 synthesis solution. These small metallic clusters showed a high stability under a harsh reaction condition without serious migration, resulting from a direct anchoring of small metallic clusters to the partially or unreduced metal ions on the surface. After a complete reduction, partial occlusion of the metallic cluster surface by amorphous silica stabilized the particles against aggregations. As a probe reaction of particle size sensitivity, carbon single wall nanotubes (SWNT) were synthesized using Co-MCM-41. A metallic cluster stability test was performed by CO methanation using Co- and Ni-MCM-41. Methanol and methane partial oxidations were carried out with V-MCM-41, and the radius of pore curvature effect on the catalytic activity was investigated

Potentiometric titration of metal ions in ethanol.

Science.gov (United States)

Gibson, Graham T T; Mohamed, Mark F; Neverov, Alexei A; Brown, R S

2006-09-18

The potentiometric titrations of Zn2+, Cu2+ and 12 Ln3+ metal ions were obtained in ethanol to determine the titration constants (defined as the at which the [-OEt]/[Mx+]t ratios are 0.5, 1.5, and 2.5) and in two cases (La3+ and Zn2+) a complete speciation diagram. Several simple monobasic acids and aminium ions were also titrated to test the validity of experimental titration measurements and to establish new constants in this medium that will be useful for the preparation of buffers and standard solutions. The dependence of the titration constants on the concentration and type of metal ion and specific counterion effects is discussed. In selected cases, the titration profiles were analyzed using a commercially available fitting program to obtain information about the species present in solution, including La3+ for which a dimer model is proposed. The fitting provides the microscopic values for deprotonation of one to four metal-bound ethanol molecules. Kinetics for the La3+-catalyzed ethanolysis of paraoxon as a function of are presented and analyzed in terms of La3+ speciation as determined by the analysis of potentiometric titration curves. The stability constants for the formation of Zn2+ and Cu2+ complexes with 1,5,9-triazacyclododecane as determined by potentiometric titration are presented.

Updated Abraham solvation parameters for polychlorinated biphenyls

NARCIS (Netherlands)

van Noort, P.C.M.; Haftka, J.J.H.; Parsons, J.R.

2010-01-01

This study shows that the recently published polychlorinated biphenyl (PCB) Abraham solvation parameters predict PCB air−n-hexadecane and n-octanol−water partition coefficients very poorly, especially for highly ortho-chlorinated congeners. Therefore, an updated set of PCB solvation parameters was

Updated Abraham solvation parameters for polychlorinated biphenyls

NARCIS (Netherlands)

Noort, van P.C.M.; Haftka, J.J.H.; Parsons, J.R.

2010-01-01

This study shows that the recently published polychlorinated biphenyl (PCB) Abraham solvation parameters predict PCB air-n-hexadecane and n-octanol-water partition coefficients very poorly, especially for highly ortho-chlorinated congeners. Therefore, an updated set of PCB solvation parameters was

Estimate of electrostatic solvation free energy of electron in various polar solvents by using modified born equation

International Nuclear Information System (INIS)

Yamashita, Kazuo; Kitamura, Mitsutaka; Imai, Hideo

1976-01-01

The modified Born equation was tentatively applied to estimate the electrostatic free energies of solvation of the electron in various polar solvents. The related data of halide ions and a datum of the hydration free energy of the electron obtained by radiation chemical studies were used for the numerical calculations. (auth.)

Removal and recovery of metal ions from process and waste streams using polymer filtration

International Nuclear Information System (INIS)

Jarvinen, G.D.; Smith, B.F.; Robison, T.W.; Kraus, K.M.; Thompson, J.A.

1999-01-01

Polymer Filtration (PF) is an innovative, selective metal removal technology. Chelating, water-soluble polymers are used to selectively bind the desired metal ions and ultrafiltration is used to concentrate the polymer-metal complex producing a permeate with low levels of the targeted metal ion. When applied to the treatment of industrial metal-bearing aqueous process streams, the permeate water can often be reused within the process and the metal ions reclaimed. This technology is applicable to many types of industrial aqueous streams with widely varying chemistries. Application of PF to aqueous streams from nuclear materials processing and electroplating operations will be described

Preferential solvation of ions in mixed solvents. 6: Univalent anions in aqueous organic solvents according to the inverse Kirkwood-Buff integral (IKBI) approach

International Nuclear Information System (INIS)

Marcus, Yizhak

2007-01-01

The inverse Kirkwood-Buff integral (IKBI) approach is applied to the preferential solvation of F - , Cl - , Br - , I - , and ClO 4 - in aqueous mixtures of the co-solvents (S) methanol (MeOH), ethanol (EtOH), t-butanol (t-BuOH), 1,2-ethanediol (EG), glycerol (Gly), acetone (Me 2 CO), acetonitrile (MeCN), formamide (FA), N,N-dimethylformamide (DMF), N,N,N',N',N'',N''-hexamethyl phosphoric triamide (HMPT), and dimethylsulfoxide (DMSO), as far as the relevant data exist in the literature. Fluoride anions are selectively solvated by the water up to large mole fractions (x S ≥ 0.4) of S = EtOH, t-BuOH, Me 2 CO, MeCN, and DMF, and up to lower contents (x S ∼ 0.1) of MeOH, EG, FA, and DMSO. The other anions are preferentially solvated by water to diminishing extent as their sizes become larger, and the largest ones show some preference for S in water-rich mixtures of MeOH and FA, whereas in aqueous Gly even chloride is preferentially solvated by the Gly. The competition between the co-solvent and the anion for the hydrogen bonds that water molecules donate is the main cause for the observed preferential solvation behaviour

Sorption of Molecular Oxygen by Metal-Ion Exchanger Nanocomposites

Science.gov (United States)

Krysanov, V. A.; Plotnikova, N. V.; Kravchenko, T. A.

2018-03-01

Kinetic features are studied of the chemisorption and reduction of molecular oxygen from water by metal-ion exchanger nanocomposites that differ in the nature of the dispersed metal and state of oxidation. In the Pd equilibrium sorption coefficient for oxygen dissolved in water ranges from 20 to 50, depending on the nature and oxidation state of the metal component.

Removal of heavy-metal ions from dilute waste streams using membrane-based hybrid systems

International Nuclear Information System (INIS)

Friesen, D.T.; Edlund, D.J.

1993-01-01

At Bend research, the authors have developed hybrid systems that couple a process that removes solvent (water) and a process that removes solute (metal ions) such that toxic heavy-metal ions can be efficiently and selectively removed to very low levels while simultaneously concentrating the heavy-metal ions in relatively pure form. Although this technology is broadly applicable, the authors are focusing on the development of a system to treat groundwater that is contaminated with heavy-metal ions. The process utilizes coupled transport and reverse osmosis to reduce chromium and uranium concentration down to parts-per-billion levels

No association between pseudotumors, high serum metal-ion levels and metal hypersensitivity in large-head metal-on-metal total hip arthroplasty at 5-7-year follow-up

DEFF Research Database (Denmark)

Hjorth, Mette Holm; Stilling, Maiken; Soballe, Kjeld

2015-01-01

-ion concentrations were measured, metal allergy and atopic dermatitis were evaluated, and the questionnaires of the Oxford Hip Score (OHS), Harris Hip Score (HHS) and the Short-Form Health Survey (SF-36) were completed. RESULTS: Pseudotumors were found in eight patients, but they were asymptomatic and their serum...... pseudotumor formation, serum metal-ion levels, metal patch test reactivity, and atopic dermatitis. However, clinicians should be aware of asymptomatic pseudotumors, and we advise further exploration into the mechanisms involved in the pathogenesis of pseudotumors.......OBJECTIVE: The relationship between metal wear debris, pseudotumor formation and metal hypersensitivity is complex and not completely understood. The purpose of this study was to assess the prevalence of pseudotumor formation in a consecutive series of metal-on-metal (MoM) total hip arthroplasty...

Metal ion reactive thin films using spray electrostatic LbL assembly.

Science.gov (United States)

Krogman, Kevin C; Lyon, Katharine F; Hammond, Paula T

2008-11-20

By using the spray-layer-by-layer (Spray-LbL) technique, the number of metal counterions trapped within LbL coatings is significantly increased by kinetically freezing the film short of equilibrium, potentially limiting interchain penetration and forcing chains to remain extrinsically compensated to a much greater degree than observed in the traditional dipped LbL technique. The basis for the enhanced entrapment of metal ions such as Cu2+, Fe2+, and Ag+ is addressed, including the equilibrium driving force for extrinsic compensation by soft versus hard metal ions and the impact of Spray-LbL on the kinetics of polymer-ion complexation. These polymer-bound metal-ion coatings are also demonstrated to be effective treatments for air filtration, functionalizing existing filters with the ability to strongly bind toxic industrial compounds such as ammonia or cyanide gases, as well as chemical warfare agent simulants such as chloroethyl ethyl sulfide. On the basis of results reported here, future work could extend this method to include other toxic soft-base ligands such as carbon monoxide, benzene, or organophosphate nerve agents.

Metal-ion catalyzed polymerization in the eutectic phase in water-ice

DEFF Research Database (Denmark)

Monnard, Pierre-Alain; Szostak, Jack W.

2008-01-01

The emergence of an RNA world requires among other processes the non-enzymatic, template-directed replication of genetic polymers such as RNA or related nucleic acids, possibly catalyzed by metal ions. The absence of uridilate derivative polymerization on adenine containing templates has been...... the main issue preventing an efficient template-directed RNA polymerization. We report here the investigation of template-directed RNA polymerization in the eutectic phase in water-ice. In particular, it was found that activated Uridilate monomers in the presence of metal-ion catalysts could efficiently......-pairing opportunities. These results suggest that a template-directed RNA polymerization catalyzed by metal-ions could be carried out under eutectic phase in water-ice conditions....

Analysis of metallic pigments by ion microbeam

International Nuclear Information System (INIS)

Pelicon, P.; Klanjsek-Gunde, M.; Kunaver, M.; Simcic, J.; Budnar, M.

2002-01-01

Metallic paints consist of metallic flakes dispersed in a resinous binder, i.e. a light-element polymer matrix. The spatial distribution and orientation of metallic flakes inside the matrix determines the covering efficiency of the paint, glossiness, and its angular-dependent properties such as lightness flop or color flop (two-tone). Such coatings are extensively used for a functional (i.e. security) as well as decorative purpose. The ion microbeam analysis of two types of silver paint with imbedded metallic flakes has been performed to determine the spatial distribution of the aluminum flakes in paint layer. The average sizes of the aluminum flakes were 23 μm (size distribution 10-37) and 49 μm (size distribution 34-75), respectively. The proton beam with the size of 2x2 μm 2 at Ljubljana ion microprobe has been used to scan the surface of the pigments. PIXE mapping of Al Kα map shows lateral distribution of the aluminum flakes, whereas the RBS slicing method reveals tomograms of the flakes in uppermost 7 μm of the pigment layer. The series of point analysis aligned over the single flake reveal the flake angle in respect to the polymer matrix surface. The angular sensitivity is well below 1 angular degree

NOTE: Ranges of ions in metals for use in particle treatment planning

Science.gov (United States)

Jäkel, Oliver

2006-05-01

In proton and ion radiotherapy, the range of particles is calculated from x-ray computed tomography (CT) numbers. Due to the strong absorption of x-rays in a metal and a cut-off for large Hounsfield units (HU) in the software of most CT-scanners, a range calculation in metals cannot be based on the measured HU. This is of special importance when metal implants such as gold fillings or hip prostheses are close to the treatment volume. In order to overcome this problem in treatment planning for heavy charged particles, the correct ranges of ions in the metal relative to water have to be assigned in the CT data. Measurements and calculations of carbon ion ranges in various metals are presented that can be used in treatment planning to allow for a more accurate range calculation of carbon ion beams in titanium, steel, tungsten and gold. The suggested values for the relative water-equivalent range and their uncertainties are 3.13 (±3%) for titanium, 5.59 (±3%) for stainless steel and 10.25 (±4%) for gold.

A review on various electrochemical techniques for heavy metal ions detection with different sensing platforms.

Science.gov (United States)

Bansod, BabanKumar; Kumar, Tejinder; Thakur, Ritula; Rana, Shakshi; Singh, Inderbir

2017-08-15

Heavy metal ions are non-biodegradable and contaminate most of the natural resources occurring in the environment including water. Some of the heavy metals including Lead (Pb), Mercury (Hg), Arsenic (As), Chromium (Cr) and Cadmium (Cd) are considered to be highly toxic and hazardous to human health even at trace levels. This leads to the requirement of fast, accurate and reliable techniques for the detection of heavy metal ions. This review presents various electrochemical detection techniques for heavy metal ions those are user friendly, low cost, provides on-site and real time monitoring as compared to other spectroscopic and optical techniques. The categorization of different electrochemical techniques is done on the basis of different types of detection signals generated due to presence of heavy metal ions in the solution matrix like current, potential, conductivity, electrochemical impedance, and electrochemiluminescence. Also, the recent trends in electrochemical detection of heavy metal ions with various types of sensing platforms including metals, metal films, metal oxides, nanomaterials, carbon nano tubes, polymers, microspheres and biomaterials have been evoked. Copyright © 2017 Elsevier B.V. All rights reserved.

Pesticides Curbing Soil Fertility: Effect of Complexation of Free Metal Ions

Science.gov (United States)

Kaur, Sukhmanpreet; Kumar, Vijay; Chawla, Mohit; Cavallo, Luigi; Poater, Albert; Upadhyay, Niraj

2017-07-01

Researchers have suggested that the reason behind infertility is pernicious effect of broad spectrum pesticides on non target, beneficial microorganism of soil. Here, studying the chelating effect of selective organophosphate and carbamate pesticides with essential metal ions, at all possible combinations of three different pH (4±0.05, 7±0.05 and 9±0.05) and three different temperatures (15±0.5°C, 30±0.5°C and 45±0.5°C), shows very fast rate of reaction which further increases with increase of pH and temperature. Carbonyl oxygen of carbamate and phosphate oxygen of organophosphate were found to be common ligating sites among all the complexes. Formed metal complexes were found to be highly stable and water insoluble on interaction with essential metal ions in solvent medium as well as over silica. Density functional theory (DFT) calculations not only reinforced the experimental observations, but, after a wide computational conformational analysis, unraveled the nature of the high stable undesired species that consist of pesticides complexed by metal ions from the soil. All in all, apart from the direct toxicity of pesticides, the indirect effect by means of complexation of free metal ions impoverishes the soil.

Pesticides Curbing Soil Fertility: Effect of Complexation of Free Metal Ions

KAUST Repository

Kaur, Sukhmanpreet

2017-07-04

Researchers have suggested that the reason behind infertility is pernicious effect of broad spectrum pesticides on non target, beneficial microorganism of soil. Here, studying the chelating effect of selective organophosphate and carbamate pesticides with essential metal ions, at all possible combinations of three different pH (4 ± 0.05, 7 ± 0.05 and 9 ± 0.05) and three different temperatures (15 ± 0.5°C, 30 ± 0.5°C and 45 ± 0.5°C), shows very fast rate of reaction which further increases with increase of pH and temperature. Carbonyl oxygen of carbamate and phosphate oxygen of organophosphate were found to be common ligating sites among all the complexes. Formed metal complexes were found to be highly stable and water insoluble on interaction with essential metal ions in solvent medium as well as over silica. Density functional theory (DFT) calculations not only reinforced the experimental observations, but, after a wide computational conformational analysis, unraveled the nature of the high stable undesired species that consist of pesticides complexed by metal ions from the soil. All in all, apart from the direct toxicity of pesticides, the indirect effect by means of complexation of free metal ions impoverishes the soil.

Pesticides Curbing Soil Fertility: Effect of Complexation of Free Metal Ions

KAUST Repository

Kaur, Sukhmanpreet; Kumar, Vijay; Chawla, Mohit; Cavallo, Luigi; Poater, Albert; Upadhyay, Niraj

2017-01-01

Researchers have suggested that the reason behind infertility is pernicious effect of broad spectrum pesticides on non target, beneficial microorganism of soil. Here, studying the chelating effect of selective organophosphate and carbamate pesticides with essential metal ions, at all possible combinations of three different pH (4 ± 0.05, 7 ± 0.05 and 9 ± 0.05) and three different temperatures (15 ± 0.5°C, 30 ± 0.5°C and 45 ± 0.5°C), shows very fast rate of reaction which further increases with increase of pH and temperature. Carbonyl oxygen of carbamate and phosphate oxygen of organophosphate were found to be common ligating sites among all the complexes. Formed metal complexes were found to be highly stable and water insoluble on interaction with essential metal ions in solvent medium as well as over silica. Density functional theory (DFT) calculations not only reinforced the experimental observations, but, after a wide computational conformational analysis, unraveled the nature of the high stable undesired species that consist of pesticides complexed by metal ions from the soil. All in all, apart from the direct toxicity of pesticides, the indirect effect by means of complexation of free metal ions impoverishes the soil.

Chemisorption of a hydrogen adatom on metal doped α-Zr (0 0 0 1 surfaces in a vacuum and an implicit solvation environment

Directory of Open Access Journals (Sweden)

Cheng Zeng

2017-12-01

Full Text Available First-principles calculations have been carried out to investigate the adsorption of a hydrogen adatom on 24 metal doped α-Zr (0 0 0 1 surfaces in both a vacuum and an implicit solvation environment. The dopant are the elements in the 4th and 5th periods in the periodic table. Doping elements at the tail of the 4th and 5th periods can significantly reduce the hydrogen pickup in a vacuum environment. A weighted d-band center theory is used to analyze the doping effect. On the other hand, the hydrogen adsorption energies in water are relatively lower for all doped slabs and the surface adsorption of hydrogen adatom is stronger than that in a vacuum environment, especially, for the slabs with doping elements at the tail of the 4th and 5th periods. In the solvation environment, electronegativity difference affects the adsorption. Doping elements Ag, Ga, Ge, Sn, and Sb can reduce the hydrogen pickup in vacuum, while Ag and Cu can reduce the hydrogen pickup of the zirconium alloys in solvent environment.

Polymer Catalysts Imprinted with Metal Ions as Biomimics of Metalloenzymes

Directory of Open Access Journals (Sweden)

Joanna Czulak

2013-01-01

Full Text Available This work presents the preparation and properties of molecularly imprinted polymers (MIPs with catalytic centers that mimic the active sites of metalloenzymes. The MIP synthesis was based on suspension polymerization of functional monomers (4-vinylpyridine and acrylonitrile with trimethylolpropane trimethacrylate as a crosslinker in the presence of transition metal ions and 4-methoxybenzyl alcohol as a template. Four metal ions have been chosen for imprinting from among the microelements that are the most essential in the native enzymes: Cu2+, Co2+, Mn2+, and Zn2+. To prepare catalysts, the required loading of metal ions was obtained during sorption process. The catalysts imprinted with Cu2+, Co2+, and Zn2+ were successfully used for hydroquinone oxidation in the presence of hydrogen peroxide. The Mn2+-imprinted catalyst showed no activity due to the insufficient metal loading. Cu2+ MIP showed the highest efficiency. In case of Cu- and Co-MIP catalysts, their activity was additionally increased by the use of surface imprinting technique.

Metal ion release from metallothioneins: proteolysis as an alternative to oxidation.

Science.gov (United States)

Peroza, Estevão A; dos Santos Cabral, Augusto; Wan, Xiaoqiong; Freisinger, Eva

2013-09-01

Metallothioneins (MTs) are among others involved in the cellular regulation of essential Zn(II) and Cu(I) ions. However, the high binding affinity of these proteins requires additional factors to promote metal ion release under physiological conditions. The mechanisms and efficiencies of these processes leave many open questions. We report here a comprehensive analysis of the Zn(II)-release properties of various MTs with special focus on members of the four main subfamilies of plant MTs. Zn(II) competition experiments with the metal ion chelator 4-(2-pyridylazo)resorcinol (PAR) in the presence of the cellular redox pair glutathione (GSH)/glutathione disulfide (GSSG) show that plant MTs from the subfamilies MT1, MT2, and MT3 are remarkably more affected by oxidative stress than those from the Ec subfamily and the well-characterized human MT2 form. In addition, we evaluated proteolytic digestion with trypsin and proteinase K as an alternative mechanism for selective promotion of metal ion release from MTs. Also here the observed percentage of liberated metal ions depends strongly on the MT form evaluated. Closer evaluation of the data additionally allowed deducing the thermodynamic and kinetic properties of the Zn(II) release processes. The Cu(I)-form of chickpea MT2 was used to exemplify that both oxidation and proteolysis are also effective ways to increase the transfer of copper ions to other molecules. Zn(II) release experiments with the individual metal-binding domains of Ec-1 from wheat grain reveal distinct differences from the full-length protein. This triggers the question about the roles of the long cysteine-free peptide stretches typical for plant MTs.

Differential geometry based solvation model II: Lagrangian formulation.

Science.gov (United States)

Chen, Zhan; Baker, Nathan A; Wei, G W

2011-12-01

Solvation is an elementary process in nature and is of paramount importance to more sophisticated chemical, biological and biomolecular processes. The understanding of solvation is an essential prerequisite for the quantitative description and analysis of biomolecular systems. This work presents a Lagrangian formulation of our differential geometry based solvation models. The Lagrangian representation of biomolecular surfaces has a few utilities/advantages. First, it provides an essential basis for biomolecular visualization, surface electrostatic potential map and visual perception of biomolecules. Additionally, it is consistent with the conventional setting of implicit solvent theories and thus, many existing theoretical algorithms and computational software packages can be directly employed. Finally, the Lagrangian representation does not need to resort to artificially enlarged van der Waals radii as often required by the Eulerian representation in solvation analysis. The main goal of the present work is to analyze the connection, similarity and difference between the Eulerian and Lagrangian formalisms of the solvation model. Such analysis is important to the understanding of the differential geometry based solvation model. The present model extends the scaled particle theory of nonpolar solvation model with a solvent-solute interaction potential. The nonpolar solvation model is completed with a Poisson-Boltzmann (PB) theory based polar solvation model. The differential geometry theory of surfaces is employed to provide a natural description of solvent-solute interfaces. The optimization of the total free energy functional, which encompasses the polar and nonpolar contributions, leads to coupled potential driven geometric flow and PB equations. Due to the development of singularities and nonsmooth manifolds in the Lagrangian representation, the resulting potential-driven geometric flow equation is embedded into the Eulerian representation for the purpose of

Electrochemical membrane reactor: In situ separation and recovery of chromic acid and metal ions

International Nuclear Information System (INIS)

Khan, Jeeshan; Tripathi, Bijay P.; Saxena, Arunima; Shahi, Vinod K.

2007-01-01

An electrochemical membrane reactor with three compartments (anolyte, catholyte and central compartment) based on in-house-prepared cation- and anion-exchange membrane was developed to achieve in situ separation and recovery of chromic acid and metal ions. The physicochemical and electrochemical properties of the ion-exchange membrane under standard operating conditions reveal its suitability for the proposed reactor. Experiments using synthetic solutions of chromate and dichromate of different concentrations were carried out to study the feasibility of the process. Electrochemical reactions occurring at the cathode and anode under operating conditions are proposed. It was observed that metal ion migrated through the cation-exchange membrane from central compartment to catholyte and OH - formation at the cathode leads to the formation of metal hydroxide. Simultaneously, chromate ion migrated through the anion-exchange membrane from central compartment to the anolyte and formed chromic acid by combining H + produced their by oxidative water splitting. Thus a continuous decay in the concentration of chromate and metal ion was observed in the central compartment, which was recovered separately in the anolyte and catholyte, respectively, from their mixed solution. This process was completely optimized in terms of operating conditions such as initial concentration of chromate and metal ions in the central compartment, the applied cell voltage, chromate and metal ion flux, recovery percentage, energy consumption, and current efficiency. It was concluded that chromic acid and metal ions can be recovered efficiently from their mixed solution leaving behind the uncharged organics and can be reused as their corresponding acid and base apart from the purifying water for further applications

Partial solvation parameters and LSER molecular descriptors

International Nuclear Information System (INIS)

Panayiotou, Costas

2012-01-01

Graphical abstract: The one-to-one correspondence of LSER molecular descriptors and partial solvation parameters (PSPs) for propionic acid. Highlights: ► Quantum-mechanics based development of a new QSPR predictive method. ► One-to-one correspondence of partial solvation parameters and LSER molecular descriptors. ► Development of alternative routes for the determination of partial solvation parameters and solubility parameters. ► Expansion and enhancement of solubility parameter approach. - Abstract: The partial solvation parameters (PSP) have been defined recently, on the basis of the insight derived from modern quantum chemical calculations, in an effort to overcome some of the inherent restrictions of the original definition of solubility parameter and expand its range of applications. The present work continues along these lines and introduces two new solvation parameters, the van der Waals and the polarity/refractivity ones, which may replace both of the former dispersion and polar PSPs. Thus, one may use either the former scheme of PSPs (dispersion, polar, acidic, and basic) or, equivalently, the new scheme (van der Waals, polarity/refractivity, acidic, basic). The new definitions are made in a simple and straightforward manner and, thus, the strength and appeal of the widely accepted concept of solubility parameter is preserved. The inter-relations of the various PSPs are critically discussed and their values are tabulated for a variety of common substances. The advantage of the new scheme of PSPs is the bridge that makes with the corresponding Abraham’s LSER descriptors. With this bridge, one may exchange information between PSPs, LSER experimental scales, and quantum mechanics calculations such as via the COSMO-RS theory. The proposed scheme is a predictive one and it is applicable to, both, homo-solvated and hetero-solvated compounds. The new scheme is tested for the calculation of activity coefficients at infinite dilution, for octanol

Preferential solvation of ions in mixed solvents. 6: Univalent anions in aqueous organic solvents according to the inverse Kirkwood-Buff integral (IKBI) approach

Energy Technology Data Exchange (ETDEWEB)

Marcus, Yizhak [Department of Inorganic and Analytical Chemistry, Hebrew University of Jerusalem, Jerusalem 91904 (Israel)], E-mail: ymarcus@vms.huji.ac.il

2007-10-15

The inverse Kirkwood-Buff integral (IKBI) approach is applied to the preferential solvation of F{sup -}, Cl{sup -}, Br{sup -}, I{sup -}, and ClO{sub 4}{sup -} in aqueous mixtures of the co-solvents (S) methanol (MeOH), ethanol (EtOH), t-butanol (t-BuOH), 1,2-ethanediol (EG), glycerol (Gly), acetone (Me{sub 2}CO), acetonitrile (MeCN), formamide (FA), N,N-dimethylformamide (DMF), N,N,N',N',N'',N''-hexamethyl phosphoric triamide (HMPT), and dimethylsulfoxide (DMSO), as far as the relevant data exist in the literature. Fluoride anions are selectively solvated by the water up to large mole fractions (x{sub S} {>=} 0.4) of S = EtOH, t-BuOH, Me{sub 2}CO, MeCN, and DMF, and up to lower contents (x{sub S} {approx} 0.1) of MeOH, EG, FA, and DMSO. The other anions are preferentially solvated by water to diminishing extent as their sizes become larger, and the largest ones show some preference for S in water-rich mixtures of MeOH and FA, whereas in aqueous Gly even chloride is preferentially solvated by the Gly. The competition between the co-solvent and the anion for the hydrogen bonds that water molecules donate is the main cause for the observed preferential solvation behaviour.

Transition metal ions mediated tyrosine based short peptide amphiphile nanostructures inhibit bacterial growth.

Science.gov (United States)

Joshi, Khashti Ballabh; Singh, Ramesh; Mishra, Narendra Kumar; Kumar, Vikas; Vinayak, Vandana

2018-05-17

We report the design and synthesis of biocompatible small peptide based molecule for the controlled and targeted delivery of the encapsulated bioactive metal ions via transforming their internal nanostructures. Tyrosine based short peptide amphiphile (sPA) was synthesized which self-assembled into β-sheet like secondary structures. The self assembly of the designed sPA was modulated by using different bioactive transition metal ions which is confirmed by spectroscopic and microscopic techniques. These bioactive metal ions conjugated sPA hybrid structures are further used to develop antibacterial materials. It is due to the excellent antibacterial activity of zinc ions that the growth of clinically relevant bacteria such as E. Coli was inhibited in the presence of zinc-sPA conjugate. The bacterial test demonstrated that owing to high biocompatibility with bacterial cell, the designed sPA worked as metal ions delivery agent and therefore it can show great potential in locally addressing bacterial infections. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamics of coproportionation reactions of homogeneous samarium (3) and yttrium (3) nitrates solvates with neutral organic phosphorus compounds

International Nuclear Information System (INIS)

Pyartman, A.K.

1995-01-01

Reaction heats of homogeneous samarium (3) and yttrium (3) nitrate solvates coproportionation with neutral organophosphoric compounds (tri-n.-butylphosphate, diisooctylmethylphosphonate, diisoamylmethylphosphonate) at T=298.15 K in hexane have been measured by thermochemical method. It has been ascertained that enthalpies of coproportionation reactions practically do not depend on the nature, concentration of rare earth metal (3) nitrate solvates in hexane, nature of neutral organophosphoric compound and constitute 1.1±-.2 kJ/mol. The Gibbs free energy of coproportionation reactions is -5.43 kJ/mol, while entropy of the reactions in 14.5±0.7 J/mol·K. 8 refs., 1 tab

Effect of transition metal ions on the conductivity and stability of stabilized zirconia

DEFF Research Database (Denmark)

Lybye, D.; Mogensen, Mogens Bjerg

2007-01-01

the effect of co-doping with smaller transition metal ions such as Ti-, Fe- and Mn-ions. Many of the ionic radii of the transition metal ions are too small compared to the host lattice ionic radius of zirconium. Here we explore the effect of a) the small ionic radii compared to the large ionic radii...

Spectrophotometric determination of some metal ions using hydrazones

International Nuclear Information System (INIS)

Mohammed, M. S.

2000-05-01

In this research many starting materials were prepared, like methyl salicylate and salicylic acid hydrazide from which different derivatives of hydrazones were synthesized by coupling with carbonyl compounds like benzil monoxime and benzil mono hydrazone which are prepared and others like salicylaldehyde and benzoin. The hydrazones that were synthesized are salicylaldehyde salicylic acid hydrazone, benzoin salicylic acid hydrazone, benzil mono hydrazone salicylic acid hydrazone and benzil monoxime salicylic acid hydrazone. These reagents were determined by different methods, IR spectrophotometric determination, the nitrogen content method and melting point determination. These hydrazones act as ligands for determination of some metal ions by making different coloured complexes that were prepared for eight hydrazones with eight metal ions U (VI), Fe (II), Fe (III), Co (II), V (II), Mo (VI), Ni (II) and Cu (II). These complexes were determined by ultraviolet and visible spectrophotometer (UV/VIS) to detect their absorbance and wavelengths (λ max). The two hydrazones salicylaldehyde salicylic acid-hydrazone and benzoin salicylic acid hydrazone, were selected for determination of five metal ions (Fe (II), Fe (III), U (VI), Ni (II) and Cu (II)), using two micelles sodium n-dodecyl sulphate and pyridinium hexa decyl bromide mono hydrate. Their absorbance and wavelengths were detected using UV/VIS spectrophotometer. (Author)

Highly ordered three-dimensional macroporous carbon spheres for determination of heavy metal ions

International Nuclear Information System (INIS)

Zhang, Yuxiao; Zhang, Jianming; Liu, Yang; Huang, Hui; Kang, Zhenhui

2012-01-01

Highlights: ► Highly ordered three dimensional macroporous carbon spheres (MPCSs) were prepared. ► MPCS was covalently modified by cysteine (MPCS–CO–Cys). ► MPCS–CO–Cys was first time used in electrochemical detection of heavy metal ions. ► Heavy metal ions such as Pb 2+ and Cd 2+ can be simultaneously determined. -- Abstract: An effective voltammetric method for detection of trace heavy metal ions using chemically modified highly ordered three dimensional macroporous carbon spheres electrode surfaces is described. The highly ordered three dimensional macroporous carbon spheres were prepared by carbonization of glucose in silica crystal bead template, followed by removal of the template. The highly ordered three dimensional macroporous carbon spheres were covalently modified by cysteine, an amino acid with high affinities towards some heavy metals. The materials were characterized by physical adsorption of nitrogen, scanning electron microscopy, and transmission electron microscopy techniques. While the Fourier-transform infrared spectroscopy was used to characterize the functional groups on the surface of carbon spheres. High sensitivity was exhibited when this material was used in electrochemical detection (square wave anodic stripping voltammetry) of heavy metal ions due to the porous structure. And the potential application for simultaneous detection of heavy metal ions was also investigated.

Metallic Sn-Based Anode Materials: Application in High-Performance Lithium-Ion and Sodium-Ion Batteries.

Science.gov (United States)

Ying, Hangjun; Han, Wei-Qiang

2017-11-01

With the fast-growing demand for green and safe energy sources, rechargeable ion batteries have gradually occupied the major current market of energy storage devices due to their advantages of high capacities, long cycling life, superior rate ability, and so on. Metallic Sn-based anodes are perceived as one of the most promising alternatives to the conventional graphite anode and have attracted great attention due to the high theoretical capacities of Sn in both lithium-ion batteries (LIBs) (994 mA h g -1 ) and sodium-ion batteries (847 mA h g -1 ). Though Sony has used Sn-Co-C nanocomposites as its commercial LIB anodes, to develop even better batteries using metallic Sn-based anodes there are still two main obstacles that must be overcome: poor cycling stability and low coulombic efficiency. In this review, the latest and most outstanding developments in metallic Sn-based anodes for LIBs and SIBs are summarized. And it covers the modification strategies including size control, alloying, and structure design to effectually improve the electrochemical properties. The superiorities and limitations are analyzed and discussed, aiming to provide an in-depth understanding of the theoretical works and practical developments of metallic Sn-based anode materials.

Ion implantation enhanced metal-Si-metal photodetectors

Science.gov (United States)

Sharma, A. K.; Scott, K. A. M.; Brueck, S. R. J.; Zolper, J. C.; Myers, D. R.

1994-05-01

The quantum efficiency and frequency response of simple Ni-Si-Ni metal-semiconductor-metal (MSM) photodetectors at long wavelengths are significantly enhanced with a simple, ion-implantation step to create a highly absorbing region approx. 1 micron below the Si surface. The internal quantum efficiency is improved by a factor of approx. 3 at 860 nm (to 64%) and a full factor of ten at 1.06 microns (to 23%) as compared with otherwise identical unimplanted devices. Dark currents are only slightly affected by the implantation process and are as low as 630 pA for a 4.5-micron gap device at 10-V bias. Dramatic improvement in the impulse response is observed, 100 ps vs. 600 ps, also at 10-V bias and 4.5-micron gap, due to the elimination of carrier diffusion tails in the implanted devices. Due to its planar structure, this device is fully VLSI compatible. Potential applications include optical interconnections for local area networks and multi-chip modules.

Hydrometallurgical recovery of metal values by the use of ion exchange

International Nuclear Information System (INIS)

Higgins, I.R.

1982-01-01

This paper presented what had been accomplished to date using Packed Bed Continuous Countercurrent Ion Exchange (CCIX) and proposed plans for more comprehensive systems that include many soluble metals of value. Frontiers of hydrometallurgy cannot be breached until advantage is taken of a multitude of metal ions in solution. The future utilization of hydrometallurgical methodology depends on the success of extraction and separation unit operations and being accepted by mining companies. Examples are presented of CCIX projects in operation and pilot plants tested as proof of the special attractive features of the Chem-Seps CCIX system. An overall plan was presented for processing of sulfide type mineralization, with emphasis on making an effort to get ''complete'' dissolution of all metals of value. Continuous Countercurrent Ion Exchange plays a vital role in hydrometallurical processing because of the need to handle prodigious volumes of solution, tremendous tonnages of salts, and to compensate for poor ion exchange equilibrium. 11 figures. (DP)

1/f Fluctuations in ion implanted metal semiconductor contacts

International Nuclear Information System (INIS)

Stojanovic, M.; Marjanovic, N.; Radojevic, B.

1998-01-01

Ion implanted Metal-Semiconductor contacts is the most widely used structures in electrical devices. Weather complete devices or some parts are of interest, properties of metal-semiconductor junction strongly influence the quality and external characteristic of electronic devices. That is the reason why special attention is paid to the investigation of factor (noise for example) that could influence given junction. Low frequency 1/f fluctuations (noise) are constantly present in metal-semiconductor junction, so measurement of their level as well as the dependence on factors such as temperature must be taken into account in detailed analysis of electrical characteristics of devices such as contact, nuclear detector with surface barrier etc. In this paper we present the results of low frequency noise level measurements on TiN-Ti-Si structures produced by As + ion implantation. (author)

Migration of metallic ions from screwposts into dentin and surrounding tissues

International Nuclear Information System (INIS)

Arvidson, K.; Wroblewski, R.

1978-01-01

Previous investigations have shown that corrosion and other electrochemical processes occur when different alloys or metals are found together in the same mouth. In the present report, when teeth were restored using non-noble metallic posts, the metals diffused out to surrounding hard and soft connective tissues. The material consisted of extracted teeth with screwposts and surrounding discolored connective tissues. The screwposts had been cemented to the teeth 3-10 years earlier. The distribution of metal ion was determined by means of energy-dispersive X-ray microanalysis. Copper and zinc were found in both hard and soft tissues. Relatively high concentrations of copper ions were identified in areas of the teeth with blue-green discolorations. Zinc ions were detected in the dentin; they most probably originated from the screwposts and the cement, but zinc is also found in normal human dentin. Copper, zinc, silver and iron were found in the dark discolorations of the gingiva adjacent to the extracted teeth. (author)

Removal of some metal ions by activated carbon prepared from Phaseolus aureus hulls.

Science.gov (United States)

Rao, M Madhava; Ramana, D K; Seshaiah, K; Wang, M C; Chien, S W Chang

2009-07-30

Removal of lead [Pb(II)], zinc [Zn(II)], copper [Cu(II)], and cadmium [Cd(II)] from aqueous solutions using activated carbon prepared from Phaseolus aureus hulls (ACPAH), an agricultural waste was studied. The influence of various parameters such as effect of pH, contact time, adsorbent dose, and initial concentration of metal ions on the removal was evaluated by batch method. The removal of metal ions by ACPAH was pH dependent and the optimum pH values were 7.0, 8.0, 7.0 and 6.0 for Cu(II), Cd(II), Zn(II), and Pb(II), respectively. The sorption isotherms were studied using Langmuir, Freundlich, Dubinin-Radushkevich (D-R), and Temkin isotherm models. The maximum adsorption capacity values of ACPAH for metal ions were 21.8 mg g(-1) for Pb(II), 21.2 mg g(-1) for Zn(II), 19.5 mg g(-1) for Cu(II), and 15.7 mg g(-1) for Cd(II). The experiments demonstrated that the removal of metal ions followed the pseudo-second-order kinetic model. Desorption experiments were carried out using HCl solution with a view to regenerate the spent adsorbent and to recover the adsorbed metal ions.

Removal of some metal ions by activated carbon prepared from Phaseolus aureus hulls

International Nuclear Information System (INIS)

Rao, M. Madhava; Ramana, D.K.; Seshaiah, K.; Wang, M.C.; Chien, S.W. Chang

2009-01-01

Removal of lead [Pb(II)], zinc [Zn(II)], copper [Cu(II)], and cadmium [Cd(II)] from aqueous solutions using activated carbon prepared from Phaseolus aureus hulls (ACPAH), an agricultural waste was studied. The influence of various parameters such as effect of pH, contact time, adsorbent dose, and initial concentration of metal ions on the removal was evaluated by batch method. The removal of metal ions by ACPAH was pH dependent and the optimum pH values were 7.0, 8.0, 7.0 and 6.0 for Cu(II), Cd(II), Zn(II), and Pb(II), respectively. The sorption isotherms were studied using Langmuir, Freundlich, Dubinin-Radushkevich (D-R), and Temkin isotherm models. The maximum adsorption capacity values of ACPAH for metal ions were 21.8 mg g -1 for Pb(II), 21.2 mg g -1 for Zn(II), 19.5 mg g -1 for Cu(II), and 15.7 mg g -1 for Cd(II). The experiments demonstrated that the removal of metal ions followed the pseudo-second-order kinetic model. Desorption experiments were carried out using HCl solution with a view to regenerate the spent adsorbent and to recover the adsorbed metal ions.

Ion mobility studies of carbohydrates as group I adducts: isomer specific collisional cross section dependence on metal ion radius.

Science.gov (United States)

Huang, Yuting; Dodds, Eric D

2013-10-15

Carbohydrates play numerous critical roles in biological systems. Characterization of oligosaccharide structures is essential to a complete understanding of their functions in biological processes; nevertheless, their structural determination remains challenging in part due to isomerism. Ion mobility spectrometry provides the means to resolve gas phase ions on the basis of their shape-to-charge ratios, thus providing significant potential for separation and differentiation of carbohydrate isomers. Here, we report on the determination of collisional cross sections for four groups of isomeric carbohydrates (including five isomeric disaccharides, four isomeric trisaccharides, two isomeric pentasaccharides, and two isomeric hexasaccharides) as their group I metal ion adducts (i.e., [M + Li](+), [M + Na](+), [M + K](+), [M + Rb](+), and [M + Cs](+)). In all, 65 collisional cross sections were measured, the great majority of which have not been previously reported. As anticipated, the collisional cross sections of the carbohydrate metal ion adducts generally increase with increasing metal ion radius; however, the collisional cross sections were found to scale with the group I cation size in isomer specific manners. Such measurements are of substantial analytical value, as they illustrate how the selection of charge carrier influences carbohydrate ion mobility determinations. For example, certain pairs of isomeric carbohydrates assume unique collisional cross sections upon binding one metal ion, but not another. On the whole, these data suggest a role for the charge carrier as a probe of carbohydrate structure and thus have significant implications for the continued development and application of ion mobility spectrometry for the distinction and resolution of isomeric carbohydrates.

Metal ion levels and lymphocyte counts

DEFF Research Database (Denmark)

Penny, Jeannette Ø; Varmarken, Jens-Erik; Ovesen, Ole

2013-01-01

BACKGROUND AND PURPOSE: Wear particles from metal-on-metal arthroplasties are under suspicion for adverse effects both locally and systemically, and the DePuy ASR Hip Resurfacing System (RHA) has above-average failure rates. We compared lymphocyte counts in RHA and total hip arthroplasty (THA) an....../ppb. INTERPRETATION: Circulating T-lymphocyte levels may decline after surgery, regardless of implant type. Metal ions-particularly cobalt-may have a general depressive effect on T- and B-lymphocyte levels. Registered with ClinicalTrials.gov under # NCT01113762.......BACKGROUND AND PURPOSE: Wear particles from metal-on-metal arthroplasties are under suspicion for adverse effects both locally and systemically, and the DePuy ASR Hip Resurfacing System (RHA) has above-average failure rates. We compared lymphocyte counts in RHA and total hip arthroplasty (THA....... RESULTS: The T-lymphocyte counts for both implant types declined over the 2-year period. This decline was statistically significant for CD3(+)CD8(+) in the THA group, with a regression coefficient of -0.04 × 10(9)cells/year (95% CI: -0.08 to -0.01). Regression analysis indicated a depressive effect...

Anisotropy enhanced X-ray scattering from solvated transition metal complexes

DEFF Research Database (Denmark)

Biasin, Elisa; van Driel, Tim B.; Levi, Gianluca

2018-01-01

Time-resolved X-ray scattering patterns from photoexcited molecules in solution are in many cases anisotropic at the ultrafast time scales accessible at X-ray free-electron lasers (XFELs). This anisotropy arises from the interaction of a linearly polarized UV-Vis pump laser pulse with the sample......, which induces anisotropic structural changes that can be captured by femtosecond X-ray pulses. In this work, a method for quantitative analysis of the anisotropic scattering signal arising from an ensemble of molecules is described, and it is demonstrated how its use can enhance the structural...... sensitivity of the time-resolved X-ray scattering experiment. This method is applied on time-resolved X-ray scattering patterns measured upon photoexcitation of a solvated di-platinum complex at an XFEL, and the key parameters involved are explored. It is shown that a combined analysis of the anisotropic...

Piezoelectric sensor for sensitive determination of metal ions based on the phosphate-modified dendrimer

Science.gov (United States)

Wang, S. H.; Shen, C. Y.; Lin, Y. M.; Du, J. C.

2016-08-01

Heavy metal ions arising from human activities are retained strongly in water; therefore public water supplies must be monitored regularly to ensure the timely detection of potential problems. A phosphate-modified dendrimer film was investigated on a quartz crystal microbalance (QCM) for sensing metal ions in water at room temperature in this study. The chemical structures and sensing properties were characterized by Fourier transform infrared spectroscopy and QCM measurement, respectively. This phosphate-modified dendrimer sensor can directly detect metal ions in aqueous solutions. This novel sensor was evaluated for its capacity to sense various metal ions. The sensor exhibited a higher sensitivity level and shorter response time to copper(II) ions than other sensors. The linear detection range of the prepared QCM based on the phosphate-modified dendrimer was 0.0001 ∼ 1 μM Cu(II) ions (R2 = 0.98). The detection properties, including sensitivity, response time, selectivity, reusability, maximum adsorption capacity, and adsorption equilibrium constants, were also investigated.

Separation of some metal ions using coupled transport supported liquid membranes

International Nuclear Information System (INIS)

Chaudhary, M.A.

1993-01-01

Liquid membrane extraction processes has become very popular due to their superiority in many ways over other separation techniques. In coupled transport membranes the metal ions can be transported across the membrane against their concentration gradient under the influence of chemical potential difference. Liquid membranes consisting of a carrier-cum-diluent, supported in microporous polymeric hydrophobic films have been studied for transport of metal ions like U(VI), Cr(VI), Be(II), V(V), Ti(IV), Zn(II), Cd(II), Hf(IV), W(VI), and Co(II). The present paper presents basic data with respect to flux and permeabilities of these metal ions across membranes based on experimental results and theoretical equations, using different carriers and diluents and provides a brief reference to possibility of such membranes for large scale applications. (author)

Linen Fire as Biosorbent to Remove Heavy Metal Ions From Wastewater Modeling

OpenAIRE

Ildar G. Shaikhiev

2014-01-01

The possibility of using linen fires – lnopererabotk i waste as a sorption material for the extraction of heavy metal ions from wastewater modeling. It is shown that treatment with acid solutions linen fires a low concentration increases the surface area of linen fires and thus sorption capacity for heavy metal ions. The values of the maximum sorption capacity ions Fe (III), Co (II), Ni (II) and Zn (II) under static and dynamic conditions. IR spectroscopy...

High intensity metallic ion beams from an ecr ion source at GANIL

International Nuclear Information System (INIS)

Leherissier, P.; Barue, C.; Canet, C.; Dupuis, M.; Flambard, J.L.; Gaubert, G.; Gibouin, S.; Huguet, Y.; Jardin, P.; Lecesne, N.; Lemagnen, F.; Leroy, R.; Pacquet, J.Y.; Pellemoine-Landre, F.; Rataud, J.P.; Jaffres, P.A.

2001-01-01

In the recent years, progress concerning the production of high intensity of metallic ions beams ( 58 Ni, 48 Ca, 76 Ge) at Ganil have been performed. The MIV0C method has been successfully used to produce a high intensity nickel beam with the ECR4 ion source: 20 eμA of 58 Ni 11+ at 24 kV extraction voltage. This beam has been maintained for 8 days and accelerated up to 74.5 MeV/u by our cyclotrons with a mean intensity of 0.13 pμA on target. This high intensity, required for experiment, led to the discovery of the doubly magic 48 Ni isotope. The oven method has been first tested with natural metallic calcium on the ECR4 ion source, then used to produce a high power beam (740 W on target i.e. 0.13 pμA accelerated up to 60 MeV/u) of 48 Ca still keeping a low consumption (0.09 mg/h). A germanium beam is now under development, using the oven method with germanium oxide. The ionization efficiencies have been measured and compared. (authors)

Observation of self-sputtering in energetic condensation of metal ions

International Nuclear Information System (INIS)

Anders, Andre

2004-01-01

The condensation of energetic metal ions on a surface may cause self-sputtering even in the absence of substrate bias. Charge-state-averaged self-sputtering yields were determined for both zirconium and gold ions generated by a cathodic vacuum arc. Films were deposited on differently biased substrates exposed to streaming Zr and Au vacuum arc plasma. The self-sputtering yields for both metals were estimated to be about 0.05 in the absence of bias, and exceeding 0.5 when bias reached-50 V. These surprisingly high values can be reconciled with binary collision theory and molecular dynamics calculations taking high the kinetic and potential energy of vacuum arc ions into account

Alkali-Metal-Ion-Functionalized Graphene Oxide as a Superior Anode Material for Sodium-Ion Batteries.

Science.gov (United States)

Wan, Fang; Li, Yu-Han; Liu, Dai-Huo; Guo, Jin-Zhi; Sun, Hai-Zhu; Zhang, Jing-Ping; Wu, Xing-Long

2016-06-06

Although graphene oxide (GO) has large interlayer spacing, it is still inappropriate to use it as an anode for sodium-ion batteries (SIBs) because of the existence of H-bonding between the layers and ultralow electrical conductivity which impedes the Na(+) and e(-) transformation. To solve these issues, chemical, thermal, and electrochemical procedures are traditionally employed to reduce GO nanosheets. However, these strategies are still unscalable, consume high amounts of energy, and are expensive for practical application. Here, for the first time, we describe the superior Na storage of unreduced GO by a simple and scalable alkali-metal-ion (Li(+) , Na(+) , K(+) )-functionalized process. The various alkali metals ions, connecting with the oxygen on GO, have played different effects on morphology, porosity, degree of disorder, and electrical conductivity, which are crucial for Na-storage capabilities. Electrochemical tests demonstrated that sodium-ion-functionalized GO (GNa) has shown outstanding Na-storage performance in terms of excellent rate capability and long-term cycle life (110 mAh g(-1) after 600 cycles at 1 A g(-1) ) owing to its high BET area, appropriate mesopore, high degree of disorder, and improved electrical conductivity. Theoretical calculations were performed using the generalized gradient approximation (GGA) to further study the Na-storage capabilities of functionalized GO. These calculations have indicated that the Na-O bond has the lowest binding energy, which is beneficial to insertion/extraction of the sodium ion, hence the GNa has shown the best Na-storage properties among all comparatives functionalized by other alkali metal ions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Divalent metal ion removal from aqueous solution by acid-treated ...

African Journals Online (AJOL)

ions determined from the Langmuir isotherm showed that C. indica had the largest sorption capacity for Pb2+ ions and the least sorption for Ni2+. The results also showed that garlic-treatment of C. indica biomass enhanced its sorption capacity for the divalent metal ions, with the enhancement factor varying from 1.22 to 1.44 ...

Sensitivity to Heavy-Metal Ions of Unfolded Fullerene Quantum Dots

Directory of Open Access Journals (Sweden)

Erica Ciotta

2017-11-01

Full Text Available A novel type of graphene-like quantum dots, synthesized by oxidation and cage-opening of C60 buckminsterfullerene, has been studied as a fluorescent and absorptive probe for heavy-metal ions. The lattice structure of such unfolded fullerene quantum dots (UFQDs is distinct from that of graphene since it includes both carbon hexagons and pentagons. The basic optical properties, however, are similar to those of regular graphene oxide quantum dots. On the other hand, UFQDs behave quite differently in the presence of heavy-metal ions, in that multiple sensitivity to Cu2+, Pb2+ and As(III was observed through comparable quenching of the fluorescent emission and different variations of the transmittance spectrum. By dynamic light scattering measurements and transmission electron microscope (TEM images we confirmed, for the first time in metal sensing, that this response is due to multiple complexation and subsequent aggregation of UFQDs. Nonetheless, the explanation of the distinct behaviour of transmittance in the presence of As(III and the formation of precipitate with Pb2+ require further studies. These differences, however, also make it possible to discriminate between the three metal ions in view of the implementation of a selective multiple sensor.

Effect Of Metal Ions On Triphenylmethane Dye Decolorization By Laccase From Trametes Versicolor

Directory of Open Access Journals (Sweden)

Chmelová Daniela

2015-12-01

Full Text Available The aim of this study was investigate the influence of different metal ions on laccase activity and triphenylmethane dye decolorization by laccase from white-rot fungus Trametes versicolor. Laccase activity was inhibited by monovalent ions (Li+, Na+, K+ and Ag+ but the presence of divalent ions increased laccase activity at the concentration of 10 mmol/l. The effect of metal ions on decolorization of triphenylmethane dyes with different structures namely Bromochlorophenol Blue, Bromophenol Blue, Bromocresol Blue and Phenol Red was tested. The presence of metal ions (Na+, K+, Mg2+, Ca2+, Ba2+, Mn2+, Zn2+ slightly decreased triphenylmethane dye decolorization by laccase from T. versicolor except Na+ and Mg2+, which caused the increase of decolorization for all tested dyes. Decolorization of selected dyes showed that the presence of low-molecular-weight compounds is necessary for effective decolorization. Hydroxybenzotriazole (HBT is the most frequently used. Although HBT belongs to most frequently used redox mediator and generally increase decolorization efficiency, so its presence decreased decolorization percentage of Bromophenol Blue and Bromochlorophenol Blue, the influence of metal ions to dye decolorization by laccase has the similar course with or without presence of redox mediator HBT.

Adsorption of heavy metal ions on molybdenum and molybdenum trioxide from dilute aqueous solution

International Nuclear Information System (INIS)

Utsunomiya, Taizo; Hoshino, Yoshio; Sakabe, Ken-ichi

1984-01-01

The adsorption of heavy metal ions such as Co(II), Cu(II) and Pb(II) on molybdenum powder has been investigated by the batch technique as a function of soaking time, concentration of heavy metal ions and coexisting salts, pH etc. Molybdenum trioxide was also used as an adsorbent for a comparison to discuss the adsorption mechanism. The amount of these heavy metal ions adsorbed was highly pH and coexisting salts dependent. These adsorbents have features of selective adsorption for Pb(II) and large adsorption rate. The adsorption of heavy metal ions on these adsorbents proceeds independently or concurrently by following complex mechanism; (1) cation exchange reaction by hydroxyl radical on the surface of Mo and MoO 3 is predominant for most of heavy metal ions except Pb(II) [Co(II), Mn(II), Fe(III), Ni(II), Zn(II), Cd(II) and Sr(II)], (2) reduction (electron exchange reaction) to low ionic or metallic state after cation exchange reaction [Cu(II) and Ag(I) on Mo] and (3) formation of a compound [Pb(II) on both Mo and MoO 3 ]. (author)

Inhibition of cellulase-catalyzed lignocellulosic hydrolysis by iron and oxidative metal ions and complexes.

Science.gov (United States)

Tejirian, Ani; Xu, Feng

2010-12-01

Enzymatic lignocellulose hydrolysis plays a key role in microbially driven carbon cycling and energy conversion and holds promise for bio-based energy and chemical industries. Cellulases (key lignocellulose-active enzymes) are prone to interference from various noncellulosic substances (e.g., metal ions). During natural cellulolysis, these substances may arise from other microbial activities or abiotic events, and during industrial cellulolysis, they may be derived from biomass feedstocks or upstream treatments. Knowledge about cellulolysis-inhibiting reactions is of importance for the microbiology of natural biomass degradation and the development of biomass conversion technology. Different metal ions, including those native to microbial activity or employed for biomass pretreatments, are often tested for enzymatic cellulolysis. Only a few metal ions act as inhibitors of cellulases, which include ferrous and ferric ions as well as cupric ion. In this study, we showed inhibition by ferrous/ferric ions as part of a more general effect from oxidative (or redox-active) metal ions and their complexes. The correlation between inhibition and oxidation potential indicated the oxidative nature of the inhibition, and the dependence on air established the catalytic role that iron ions played in mediating the dioxygen inhibition of cellulolysis. Individual cellulases showed different susceptibilities to inhibition. It is likely that the inhibition exerted its effect more on cellulose than on cellulase. Strong iron ion chelators and polyethylene glycols could mitigate the inhibition. Potential microbiological and industrial implications of the observed effect of redox-active metal ions on enzymatic cellulolysis, as well as the prevention and mitigation of this effect in industrial biomass conversion, are discussed.

Highly ordered three-dimensional macroporous carbon spheres for determination of heavy metal ions

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yuxiao; Zhang, Jianming [Institute of Functional Nano and Soft Materials (FUNSOM) and Jiangsu Key Laboratory for Carbon-Based Functional Materials and Devices, Soochow University, Suzhou 215123 (China); Liu, Yang, E-mail: yangl@suda.edu.cn [Institute of Functional Nano and Soft Materials (FUNSOM) and Jiangsu Key Laboratory for Carbon-Based Functional Materials and Devices, Soochow University, Suzhou 215123 (China); Huang, Hui [Institute of Functional Nano and Soft Materials (FUNSOM) and Jiangsu Key Laboratory for Carbon-Based Functional Materials and Devices, Soochow University, Suzhou 215123 (China); Kang, Zhenhui, E-mail: zhkang@suda.edu.cn [Institute of Functional Nano and Soft Materials (FUNSOM) and Jiangsu Key Laboratory for Carbon-Based Functional Materials and Devices, Soochow University, Suzhou 215123 (China)

2012-04-15

Highlights: Black-Right-Pointing-Pointer Highly ordered three dimensional macroporous carbon spheres (MPCSs) were prepared. Black-Right-Pointing-Pointer MPCS was covalently modified by cysteine (MPCS-CO-Cys). Black-Right-Pointing-Pointer MPCS-CO-Cys was first time used in electrochemical detection of heavy metal ions. Black-Right-Pointing-Pointer Heavy metal ions such as Pb{sup 2+} and Cd{sup 2+} can be simultaneously determined. -- Abstract: An effective voltammetric method for detection of trace heavy metal ions using chemically modified highly ordered three dimensional macroporous carbon spheres electrode surfaces is described. The highly ordered three dimensional macroporous carbon spheres were prepared by carbonization of glucose in silica crystal bead template, followed by removal of the template. The highly ordered three dimensional macroporous carbon spheres were covalently modified by cysteine, an amino acid with high affinities towards some heavy metals. The materials were characterized by physical adsorption of nitrogen, scanning electron microscopy, and transmission electron microscopy techniques. While the Fourier-transform infrared spectroscopy was used to characterize the functional groups on the surface of carbon spheres. High sensitivity was exhibited when this material was used in electrochemical detection (square wave anodic stripping voltammetry) of heavy metal ions due to the porous structure. And the potential application for simultaneous detection of heavy metal ions was also investigated.

A shell-resolved analysis of preferential solvation of coffee ingredients in aqueous mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate

Science.gov (United States)

Zeindlhofer, Veronika; Berger, Magdalena; Steinhauser, Othmar; Schröder, Christian

2018-05-01

Ionic liquids increase the solubility of various coffee ingredients in aqueous solution but little is known about the underlying mechanism. Kirkwood-Buff integrals as well as the potential of mean force indicate that the imidazolium cations are accumulated at the surface of the solutes, removing water molecules from the solute surface. Although hydrogen bonding of the anions to hydroxy groups of the solutes can be detected, their concentration at the surface is less enhanced compared to the cations. The decomposition into solvation shells by Voronoi tessellation reveals that structural features are only observed in the first solvation shell. Nevertheless, the depletion of water and the excess concentration of the ions and, in particular, of the cations are visible in the next solvation shells as well. Therefore, classical arguments of hydrotropic theory fail to explain this behavior.

Solvated electron structure in glassy matrices

International Nuclear Information System (INIS)

Kevan, L.

1981-01-01

Current knowledge of the detailed geometrical structure of solvated electrons in aqueous and organic media is summarized. The geometry of solvated electrons in glassy methanol, ethanol, and 2-methyltetrahydrofuran is discussed. Advanced electron magnetic resonance methods and development of new methods of analysis of electron spin echo modulation patterns, second moment line shapes, and forbidden photon spin-flip transitions for paramagnetic species in these disordered systems are discussed. 66 references are cited

Equilibrium and kinetics studies of metal ion adsorption on dyed ...

African Journals Online (AJOL)

GREGO

2007-04-02

Apr 2, 2007 ... Initial concentration of Cu(II) ions = 20 mg/l, adsorbent dose = 1.0 g. Table 2 Experiment Data of ... diffusivity of the metal ion would be independent of the extent of sorption .... exchange and adsorption. Equilibrium parameter.

Lithium alloys and metal oxides as high-capacity anode materials for lithium-ion batteries

International Nuclear Information System (INIS)

Liang, Chu; Gao, Mingxia; Pan, Hongge; Liu, Yongfeng; Yan, Mi

2013-01-01

Highlights: •Progress in lithium alloys and metal oxides as anode materials for lithium-ion batteries is reviewed. •Electrochemical characteristics and lithium storage mechanisms of lithium alloys and metal oxides are summarized. •Strategies for improving electrochemical lithium storage properties of lithium alloys and metal oxides are discussed. •Challenges in developing lithium alloys and metal oxides as commercial anodes for lithium-ion batteries are pointed out. -- Abstract: Lithium alloys and metal oxides have been widely recognized as the next-generation anode materials for lithium-ion batteries with high energy density and high power density. A variety of lithium alloys and metal oxides have been explored as alternatives to the commercial carbonaceous anodes. The electrochemical characteristics of silicon, tin, tin oxide, iron oxides, cobalt oxides, copper oxides, and so on are systematically summarized. In this review, it is not the scope to retrace the overall studies, but rather to highlight the electrochemical performances, the lithium storage mechanism and the strategies in improving the electrochemical properties of lithium alloys and metal oxides. The challenges and new directions in developing lithium alloys and metal oxides as commercial anodes for the next-generation lithium-ion batteries are also discussed

Photodetachment of negative ion in a gradient electric field near a metal surface

International Nuclear Information System (INIS)

Liu Tian-Qi; Wang De-Hua; Han Cai; Liu Jiang; Liang Dong-Qi; Xie Si-Cheng

2012-01-01

Based on closed-orbit theory, the photodetachment of H − in a gradient electric field near a metal surface is studied. It is demonstrated that the gradient electric field has a significant influence on the photodetachment of negative ions near a metal surface. With the increase of the gradient of the electric field, the oscillation in the photodetachment cross section becomes strengthened. Besides, in contrast to the photodetachment of H − near a metal surface in a uniform electric field, the oscillating amplitude and the oscillating region in the cross section of a gradient electric field also become enlarged. Therefore, we can use the gradient electric field to control the photodetachment of negative ions near a metal surface. We hope that our results will be useful for understanding the photodetachment of negative ions in the vicinity of surfaces, cavities, and ion traps. (atomic and molecular physics)

Copper-transporting P-type ATPases use a unique ion-release pathway

DEFF Research Database (Denmark)

Andersson, Magnus; Mattle, Daniel; Sitsel, Oleg

2014-01-01

Heavy metals in cells are typically regulated by PIB-type ATPases. The first structure of the class, a Cu(+)-ATPase from Legionella pneumophila (LpCopA), outlined a copper transport pathway across the membrane, which was inferred to be occluded. Here we show by molecular dynamics simulations...... that extracellular water solvated the transmembrane (TM) domain, results indicative of a Cu(+)-release pathway. Furthermore, a new LpCopA crystal structure determined at 2.8-Å resolution, trapped in the preceding E2P state, delineated the same passage, and site-directed-mutagenesis activity assays support...... a functional role for the conduit. The structural similarities between the TM domains of the two conformations suggest that Cu(+)-ATPases couple dephosphorylation and ion extrusion differently than do the well-characterized PII-type ATPases. The ion pathway explains why certain Menkes' and Wilson's disease...

Density functional study of isoguanine tetrad and pentad sandwich complexes with alkali metal ions.

Science.gov (United States)

Meyer, Michael; Steinke, Thomas; Sühnel, Jürgen

2007-02-01

Isoguanine tetraplexes and pentaplexes contain two or more stacked polyads with intercalating metal ions. We report here the results of a density functional study of sandwiched isoguanine tetrad and pentad complexes consisting of two polyads with Na(+), K(+) and Rb(+) ions at the B3LYP level. In comparison to single polyad metal ion complexes, there is a trend towards increased non-planarity of the polyads in the sandwich complexes. In general, the pentad sandwiches have relatively planar polyad structures, whereas the tetrad complexes contain highly non-planar polyad building blocks. As in other sandwich complexes and in metal ion complexes with single polyads, the metal ion-base interaction energy plays an essential role. In iG sandwich structures, this interaction energy is slightly larger than in the corresponding guanine sandwich complexes. Because the base-base interaction energy is even more increased in passing from guanine to isoguanine, the isoguanine sandwiches are thus far the only examples where the base-base interaction energy is larger than the base-metal ion interaction energy. Stacking interactions have been studied in smaller models consisting of two bases, retaining the geometry from the complete complex structures. From the data obtained at the B3LYP and BH&H levels and with Møller-Plesset perturbation theory, one can conclude that the B3LYP method overestimates the repulsion in stacked base dimers. For the complexes studied in this work, this is only of minor importance because the direct inter-tetrad or inter-pentad interaction is supplemented by a strong metal ion-base interaction. Using a microsolvation model, the metal ion preference K(+) approximately Rb(+) > Na(+) is found for tetrad complexes. On the other hand, for pentads the ordering is Rb(+) > K(+) > Na(+). In the latter case experimental data are available that agree with this prediction.

Ion spectra of the metal vapor vacuum arc ion source with compound and alloy cathodes

Science.gov (United States)

Sasaki, Jun; Brown, Ian G.

1990-01-01

In metal vapor vacuum arc (MEVVA) ion sources, vacuum arc plasma with cathodes of single, pure elements has been utilized for the production of metal ions. In this study, we have investigated the charge state distributions of ions produced in vacuum arc plasmas in a MEVVA ion source for the case when the cathode is an alloy or a compound material. The ion charge state spectra were analyzed by means of a time-of-flight apparatus. We have compared the ion spectra for a cathode of an alloy or a compound material with its constituent elements: TiC/TiN/TiO2/Ti/C, SiC/Si/C, WC/W/C U/UN/(UN-ZrC)/Zr/C, and brass/Zn/Cu. We find that the MEVVA produces ions of all constituent elements in the compound and the alloy cathodes. The charge state distribution of each element differs, however, from the charge state distribution obtained in the vacuum arc with a cathode made of the pure, single constituent element. Fractional values of the total ion numbers of each constituent element in the extracted beam depart from the stoichiometry of the elements in the cathode material. In an operation with a TiC cathode, we irradiated a 304 stainless-steel plate with the extracted beam. Results from glow-discharge spectroscopy (GDS) of the surface show that both titanium and carbon are implanted in the substrate after the irradiation.

Examining metallic glass formation in LaCe:Nb by ion implantation

Directory of Open Access Journals (Sweden)

Sisson Richard

2017-01-01

Full Text Available In order to combine niobium (Nb with lanthanum (La and cerium (Ce, Nb ions were deposited within a thin film of these two elements. According to the Hume-Rothery rules, these elements cannot be combined into a traditional crystalline metallic solid. The creation of an amorphous metallic glass consisting of Nb, La, and Ce is then investigated. Amorphous metallic glasses are traditionally made using fast cooling of a solution of molten metals. In this paper, we show the results of an experiment carried out to form a metallic glass by implanting 9 MeV Nb 3+ atoms into a thin film of La and Ce. Prior to implantation, the ion volume distribution is calculated by Monte Carlo simulation using the SRIM tool suite. Using multiple methods of electron microscopy and material characterization, small quantities of amorphous metallic glass are indeed identified.

Study of highly functionalized metal surface treated by plasma ion implantation

International Nuclear Information System (INIS)

Ikeyama, Masami; Miyagawa, Soji; Miyagawa, Yoshiko; Nakao, Setsuo; Masuda, Haruho; Saito, Kazuo; Ono, Taizou; Hayashi, Eiji

2004-01-01

Technology for processing metal surfaces with hardness, low friction and free from foreign substances was developed with plasma ion implantation. Diamond-like carbon (DLC) coating is a most promising method for realization of hard and smooth metal surface. DLC coating was tested in a metal pipe with 10 mm diameter and 10 cm length by a newly developed plasma ion implantation instrument. The surface coated by DLC was proved to have characteristics equivalent to those prepared with other methods. A computer program simulating a formation process of DLC coating was developed. Experiments for fluorinating the DLC coating surface was performed. (Y. Kazumata)

Studies of base pair sequence effects on DNA solvation based on all-atom molecular dynamics simulations.

Science.gov (United States)

Dixit, Surjit B; Mezei, Mihaly; Beveridge, David L

2012-07-01

Detailed analyses of the sequence-dependent solvation and ion atmosphere of DNA are presented based on molecular dynamics (MD) simulations on all the 136 unique tetranucleotide steps obtained by the ABC consortium using the AMBER suite of programs. Significant sequence effects on solvation and ion localization were observed in these simulations. The results were compared to essentially all known experimental data on the subject. Proximity analysis was employed to highlight the sequence dependent differences in solvation and ion localization properties in the grooves of DNA. Comparison of the MD-calculated DNA structure with canonical A- and B-forms supports the idea that the G/C-rich sequences are closer to canonical A- than B-form structures, while the reverse is true for the poly A sequences, with the exception of the alternating ATAT sequence. Analysis of hydration density maps reveals that the flexibility of solute molecule has a significant effect on the nature of observed hydration. Energetic analysis of solute-solvent interactions based on proximity analysis of solvent reveals that the GC or CG base pairs interact more strongly with water molecules in the minor groove of DNA that the AT or TA base pairs, while the interactions of the AT or TA pairs in the major groove are stronger than those of the GC or CG pairs. Computation of solvent-accessible surface area of the nucleotide units in the simulated trajectories reveals that the similarity with results derived from analysis of a database of crystallographic structures is excellent. The MD trajectories tend to follow Manning's counterion condensation theory, presenting a region of condensed counterions within a radius of about 17 A from the DNA surface independent of sequence. The GC and CG pairs tend to associate with cations in the major groove of the DNA structure to a greater extent than the AT and TA pairs. Cation association is more frequent in the minor groove of AT than the GC pairs. In general, the

Large pore bi-functionalised mesoporous silica for metal ion pollution treatment

International Nuclear Information System (INIS)

Burke, Aoife M.; Hanrahan, John P.; Healy, David A.; Sodeau, John R.; Holmes, Justin D.; Morris, Michael A.

2009-01-01

Here we demonstrate aminopropyl and mercatopropyl functionalised and bi-functionalised large pore mesoporous silica spheres to extract various metal ions from aqueous solutions towards providing active sorbents for mitigation of metal ion pollution. Elemental analysis (EA) and FTIR techniques were used to quantify the attachment of the aminopropyl and mercatopropyl functional groups to the mesoporous silica pore wall. Functionalisation was achieved by post-synthesis reflux procedures. For all functionalised silicas the functionalisation refluxing does not alter particle morphology/agglomeration of the particles. It was found that sorptive capacities of the mesoporous silica towards the functional groups were unaffected by co-functionalisation. Powder X-ray diffraction (PXRD) and nitrogen adsorption techniques were used to establish the pore diameters, packing of the pores and specific surface areas of the modified mesoporous silica spheres. Atomic absorption (AA) spectroscopy and inductively coupled plasma-atomic emission spectrometry (ICP-AES) techniques were used to measure the extraction efficiencies of each metal ion species from solution at varying pHs. Maximum sorptive capacities (as metal ions) were determined to be 384 μmol g -1 for Cr, 340 μmol g -1 for Ni, 358 μmol g -1 for Fe, 364 μmol g -1 for Mn and 188 μmol g -1 for Pd

Large pore bi-functionalised mesoporous silica for metal ion pollution treatment

Energy Technology Data Exchange (ETDEWEB)

Burke, Aoife M.; Hanrahan, John P. [Department of Chemistry, Materials Section and Supercritical Fluid Centre, University College Cork, Cork (Ireland); Environmental Research Institute (ERI), Lee Road, Cork (Ireland); Healy, David A.; Sodeau, John R. [Department of Chemistry, Centre of Research in Atmospheric Chemistry, University College Cork, Cork (Ireland); Holmes, Justin D. [Department of Chemistry, Materials Section and Supercritical Fluid Centre, University College Cork, Cork (Ireland); Centre for Research on Adaptive Nanostructures and Nanodevices (CRANN), Trinity College Dublin, Dublin 2 (Ireland); Morris, Michael A. [Department of Chemistry, Materials Section and Supercritical Fluid Centre, University College Cork, Cork (Ireland); Environmental Research Institute (ERI), Lee Road, Cork (Ireland); Centre for Research on Adaptive Nanostructures and Nanodevices (CRANN), Trinity College Dublin, Dublin 2 (Ireland)], E-mail: m.morris@ucc.ie

2009-05-15

Here we demonstrate aminopropyl and mercatopropyl functionalised and bi-functionalised large pore mesoporous silica spheres to extract various metal ions from aqueous solutions towards providing active sorbents for mitigation of metal ion pollution. Elemental analysis (EA) and FTIR techniques were used to quantify the attachment of the aminopropyl and mercatopropyl functional groups to the mesoporous silica pore wall. Functionalisation was achieved by post-synthesis reflux procedures. For all functionalised silicas the functionalisation refluxing does not alter particle morphology/agglomeration of the particles. It was found that sorptive capacities of the mesoporous silica towards the functional groups were unaffected by co-functionalisation. Powder X-ray diffraction (PXRD) and nitrogen adsorption techniques were used to establish the pore diameters, packing of the pores and specific surface areas of the modified mesoporous silica spheres. Atomic absorption (AA) spectroscopy and inductively coupled plasma-atomic emission spectrometry (ICP-AES) techniques were used to measure the extraction efficiencies of each metal ion species from solution at varying pHs. Maximum sorptive capacities (as metal ions) were determined to be 384 {mu}mol g{sup -1} for Cr, 340 {mu}mol g{sup -1} for Ni, 358 {mu}mol g{sup -1} for Fe, 364 {mu}mol g{sup -1} for Mn and 188 {mu}mol g{sup -1} for Pd.

Molecular Dynamics Simulations on the solvation and interfacial behaviour of hydrophobic species. Applications to the TATB hypothesis and to the liquid/liquid extraction of cations to supercritical CO2

International Nuclear Information System (INIS)

Schurhammer, R.

2001-12-01

We report molecular dynamics studies on the solvation of charged hydrophobic molecules in pure liquids and at liquid / liquid interfaces. The first part of the thesis deals with the TATB hypothesis according to which the Asφ 4 + (TA + ) and Bφ 4 - (TB - ) ions have the same free energy of solvation in any solvent. The two ions are found to be solvated differently in pure liquids (water, chloroform, acetonitrile) as at a chloroform / water interface. These results are confirmed by free energy calculations and by simulations on iso-volume spherical S + and S - ions, which perfectly meet the TATB criteria. The many methodological tests performed show the importance of (i) the corrected treatment of 'long range interactions' (ii) the precise repartition of atomic charges (iii) the solvent models, especially for water, on the + / - charge discrimination by solvent. In the second part, in relation to the liquid / liquid extraction of cations from water to supercritical CO 2 , we report the behaviour of ions (Cs + , UO 2 2+ , Eu 3+ ), of un-complexed extractants molecules (tri-n-butylphosphate, calixarene), of their complexes with the cations and nitric acid at a preformed chloroform / water interface and during de-mixing simulations which started from a perfectly mixed CO 2 / water solutions. These studies demonstrate the importance of interfacial phenomena, of simulation conditions and acid and extractant concentrations, in assisted ion extraction to supercritical CO 2 . (author)

The influence of heavy metals on the production of extracellular polymer substances in the processes of heavy metal ions elimination.

Science.gov (United States)

Mikes, J; Siglova, M; Cejkova, A; Masak, J; Jirku, V

2005-01-01

Wastewaters from a chemical industry polluted by heavy metal ions represent a hazard for all living organisms. It can mean danger for ecosystems and human health. New methods are sought alternative to traditional chemical and physical processes. Active elimination process of heavy metals ions provided by living cells, their components and extracellular products represents a potential way of separating toxic heavy metals from industrial wastewaters. While the abilities of bacteria to remove metal ions in solution are extensively used, fungi have been recognized as a promising kind of low-cost adsorbents for removal of heavy-metal ions from aqueous waste sources. Yeasts and fungi differ from each other in their constitution and in their abilities to produce variety of extracellular polymeric substances (EPS) with different mechanisms of metal interactions. The accumulation of Cd(2+), Cr(6+), Pb(2+), Ni(2+) and Zn(2+) by yeasts and their EPS was screened at twelve different yeast species in microcultivation system Bioscreen C and in the shaking Erlenmayer's flasks. This results were compared with the production of yeast EPS and the composition of yeast cell walls. The EPS production was measured during the yeast growth and cell wall composition was studied during the cultivations in the shaking flasks. At the end of the process extracellular polymers and their chemical composition were isolated and amount of bound heavy metals was characterized. The variable composition and the amount of the EPS were found at various yeast strains. It was influenced by various compositions of growth medium and also by various concentrations of heavy metals. It is evident, that the amount of bound heavy metals was different. The work reviews the possibilities of usage of various yeast EPS and components of cell walls in the elimination processes of heavy metal ions. Further the structure and properties of yeasts cell wall and EPS were discussed. The finding of mechanisms mentioned

Mechanism of Metal Ion Activation of the Diphtheria Toxin Repressor DtxR

Energy Technology Data Exchange (ETDEWEB)

D' Aquino,J.; Tetenbaum-Novatt, J.; White, A.; Berkovitch, F.; Ringe, D.

2005-01-01

The diphtheria toxin repressor (DtxR) is a metal ion-activated transcriptional regulator that has been linked to the virulence of Corynebacterium diphtheriae. Structure determination has shown that there are two metal ion binding sites per repressor monomer, and site-directed mutagenesis has demonstrated that binding site 2 (primary) is essential for recognition of the target DNA repressor, leaving the role of binding site 1 (ancillary) unclear. Calorimetric techniques have demonstrated that although binding site 1 (ancillary) has high affinity for metal ion with a binding constant of 2 x 10{sup -7}, binding site 2 (primary) is a low-affinity binding site with a binding constant of 6.3 x 10{sup -4}. These two binding sites act in an independent fashion, and their contribution can be easily dissected by traditional mutational analysis. Our results clearly demonstrate that binding site 1 (ancillary) is the first one to be occupied during metal ion activation, playing a critical role in stabilization of the repressor. In addition, structural data obtained for the mutants Ni-DtxR(H79A, C102D), reported here, and the previously reported DtxR(H79A) have allowed us to propose a mechanism of metal activation for DtxR.

Rapid heating evaporation of Pb(NO3)2. Evidence for heterogeneous ion-molecule reactions

International Nuclear Information System (INIS)

Radus, T.P.; Udseth, H.R.; Friedman, L.

1979-01-01

A mass spectrometric investigation of the lead nitrate system is reported in which the lead nitrate was evaporated from a probe filament that was heated as rapidly as 5000 0 C/s. Both electron impact (EI) and chemical ionization (CI) source techniques were used in this study. Fragment ions and decomposition products were observed under EI conditions. Under CI conditions solvated fragment ions and protonated solvated molecular ions were detected. Temperature measurements of rates of evaporation were made by monitoring the resistance of the probe filament as it was heated. Activation energies calculated by using these temperature coefficients of evaporation rates indicate that evaporations under CI conditions are assisted by heterogeneous ion-molecule reactions

Tailoring of the PS surface with low energy ions: Relevance to growth and adhesion of noble metals

International Nuclear Information System (INIS)

Zaporojtchenko, V.; Zekonyte, J.; Wille, S.; Schuermann, U.; Faupel, F.

2005-01-01

Ion-polymer interaction induces different phenomena in the near surface layer of polymers, and promotes its adhesion to metals. Using XPS, TEM and AFM, polystyrene surface was examined after 1 keV ion-beam treatments with oxygen, nitrogen and argon ions in the ion fluence range from 10 12 to 10 16 cm -2 to clarify the following points: chemical reaction after treatment in vacuum and after exposure to air, identification of adsorption-relevant species for metal atoms, formation of cross-links in the outermost polymer layer. The early stages of metal-polymer interface formation during metallization play a crucial role in the metal-polymer adhesion. Therefore, the influence of the ion fluence and ion chemistry on the condensation of noble metals, film growth and peel strength were measured. The peel strength showed a maximum at a certain fluence depending on ion chemistry. For example, the surface treatment with very low fluence of oxygen ions improved the adhesion between copper and polystyrene by two orders of magnitude without significantly increasing the surface roughness measured with AFM. The locus of failure changed at the same time from interfacial failure for untreated polymer surfaces to cohesive failure in the polymer for modified surfaces. A multilayer model of the metal-polymer interface after ion treatment is suggested

Selective chelation-supercritical fluid extraction of metal ions from waste materials

International Nuclear Information System (INIS)

Wai, C.N.; Laintz, K.E.; Yonker, C.R.

1993-01-01

The removal of toxic organics, metals, and radioisotopes from solids or liquids is a major concern in the treatment of industrial and nuclear wastes. For this reason, developing methods for selective separation of toxic metals and radioactive materials from solutions of complex matrix is an important problem in environmental research. Recent developments indicate supercritical fluids are good solvents for organic compounds. Many gases become supercritical fluids under moderate temperatures and pressures. For example, the critical temperature and pressure of carbon dioxide are 31 degrees C and 73 atm, respectively. The high diffusivity, low viscosity, and T-P dependence of solvent strength are some attractive properties of supercritical fluid extraction (SFE). Since CO 2 offers the additional benefits of stability and non-toxicity, the SFE technique avoids generation of organic liquid waste and exposure of personnel to toxic solvents. While direct extraction of metal ions by supercritical fluids is highly inefficient, these ions when complexed with organic ligands become quite soluble in supercritical fluids. Specific ligands can be used to achieve selective extraction of metal ions in this process. After SFE, the fluid phase can be depressurized for precipitation of the metal chelates and recycled. The ligand can also be regenerated for repeated use. The success of this selective chelation-supercritical fluid extraction (SC-SFE) process depends on a number of factors including the efficiencies of the selective chelating agents, solubilities of metal chelates in supercritical fluids, rate of extraction, ease of regeneration of the ligands, etc. In this report, the authors present recent results on the studies of the solubilities of metal chelates in supercritical CO 2 , experimental ions from aqueous solution, and the development of selective chelating agents (ionizable crown ethers) for the extraction of lanthanides and actinides