Synthesis of Y-type zeolites with high degree of Na<Superscript>+</Superscript> cation exchange for La<Superscript>3+</Superscript>

Effect of parameters of the ion exchange of Na⁺ cations for La³⁺ in Y zeolites with SiO₂/Al₂O₃ molar ratios of 5.1 and 6.0 on the degree of exchange and physicochemical properties of the resulting LaNaY samples was studied. The conditions in which deeply substituted La-forms of a Y zeolite with high degree of crystallinity can be obtained were determined.     

Theoretical investigation on the gas phase decomposition of ethyl acetate by Ni<Superscript>+</Superscript>

The density functional theory calculations were performed to systematically investigate the reaction of Ni⁺ with ethyl acetate in the gas phase. The reactive sites and reactivity were predicted by the average local ionization energy (ALIE). All possible reaction pathways were identified, which led to the formation of ketene or ethanol, two acetal units, and acetic acid or ethylene. The product distribution was discussed by means of the Curtin-Hammett principle. In addition, the properties of the chemical bonding evolution along the reaction pathway were studied using various analysis methods including atoms in molecules (AIM) and natural bond orbital (NBO). The frontier molecular orbital interactions were analyzed. The calculation results confirm that there are three reaction paths, in which the path B is the most favorable path, and acetic acid or ethylene is the main product.

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Kinetic aspects of the ion-exchange reactions of Cs<Superscript>+</Superscript>, Na<Superscript>+</Superscript>, Sr<Superscript>2+</Superscript>and Eu<Superscript>2+</Superscript> ions on the H<Superscript>+</Superscript> form of chromium hexacyanoferrate(II)

Summary This paper reports the radiochemical study of the ion-exchange of Cs⁺, Na⁺, Sr²⁺ and Eu³⁺ ions with H⁺ by chromium hexacyanoferrate(II) which was prepared in a granular form using a gel method. The slow steps which determine the rate of exchange of these ions are directly proportional to the particle diameter and this is confirmed from the linearity test of Bt vs. t plots at different particle diameters. Boyed’s equation and Reichenberg’s tables were used for evaluating all the kinetic parameters. The results reveal that the effective particle radii are unchanged for both chromium hexacyanoferrate(II) dried at 60 and 120 °C. The obtained data were analyzed using McKay plots and Arrhenius equation and the kinetic and thermodynamic parameters, e.g., effective diffusion coefficient, activation energies and entropies of activation have been evaluated. The mobility of these ions inside the particles of chromium hexacyanoferrate(II) decrease in the order of Eu³⁺>Sr²⁺>Na⁺⊃Cs⁺.     

Interaction energies of histidine with cations (H<Superscript>+</Superscript>, Li<Superscript>+</Superscript>, Na<Superscript>+</Superscript>, K<Superscript>+</Superscript>, Mg<Superscript>2+</Superscript>, Ca<Superscript>2+</Superscript>)

The imidazol side group of histidine has two nitrogen atoms capable of being protonated or participating in metal binding. Hence, histidine can take on various metal-bound and protonated forms in proteins. Because of its variable structural state, histidine often functions as a key amino acid residue in enzymatic reactions. Ab initio (HF and MP2) calculations were done in modeling the cation (H⁺, Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺) interaction with side chain of histidine. The region selectivity of metal ion complexation is controlled by the affinity of the side of attack. In the imidazol unite of histidine the ring nitrogen has much higher metal ion (as well as proton) affinity. The complexation energies with the model systems decrease in the following order: Mg²⁺ > Ca²⁺ > Li⁺ > Na⁺ > K⁺. The variation of the bond lengths and the extent of charge transfer upon complexation correlate well with the computed interaction energies.     

Theoretical study on the reactions of Zr<Superscript>+</Superscript> and Zr with CO<Subscript>2</Subscript> in gas phase

Density functional theory (DFT) calculations have been performed to explore the potential energy surfaces of C-O bond activation in CO₂ molecule by gas-phase Zr⁺ cation and Zr atom, for better understanding the mechanism of second-row transition metal reacting with CO₂. The minimum energy reaction path is found to involve the spin inversion in the different reaction steps. This potential energy curvecrossing dramatically affects reaction energetics. The present results show that the reaction mechanism is insertion-elimination mechanism along the C-O bond activation. All theoretical results not only support the existing conclusions inferred from early experiment, but also complement the pathway and mechanism for this reaction.     

Theoretical investigation on cyclohexane dehydrogenation catalyzed by V<Subscript>2</Subscript><Superscript>+</Superscript> in gas-phase

The dehydrogenation reaction mechanism of cyclohexane catalyzed by dimer transition metal cluster V₂⁺ has been investigated at the B3LYP/6-31G (d, p) level of density functional theory. Density of states (DOS) graph is used to understand more deeply the roles of the front molecular orbital of the initial complexes. After the first molecular dehydrogenation, the reaction mainly consists of two competition mechanisms. First, the C-H bonds of cyclohexane can be effectively activated by the V₂⁺ cation, yielding the same-face dehydrogenation products. Second, the C-C bonds are activated, forming the different-face dehydrogenation products. Our calculations indicate that the reaction takes place more easily along the low-spin potential energy surface on the same-face and is a low-barrier or even barrier-free transformation. Carbon-carbon single bonds are nonpolar and generally far less reactive. A comparison of the reaction mechanism of V₂⁺ and congener Ti₂⁺ with cyclohexane has been presented. The bond dissociation energies (BDEs) of V₂⁺ are greater than that of Ti₂⁺, leading to difficulties in forming sandwich complexes in the different-face dehydrogenation of cyclohexane, and the same-face dehydrogenation is an important reaction channel.     

Dynamics of the Na<Superscript>+</Superscript>-Ca<Superscript>2+</Superscript> exchange on a carboxy cation exchanger

Nonequilibrium dynamics of the Na⁺-Ca²⁺ exchange in water softening on a Lewatit CNP 80 carboxylic cation-exchanger was studied at a widely varying linear velocity of water filtration. The kinetic coefficient of the pore-diffusion mass-transfer was determined at various flow rates of the model solution.     

Effects of La<Superscript>3+</Superscript> on inward K<Superscript>+</Superscript> channels at plasma membrane in guard cells

The effects of La³⁺ on inward K⁺ channels at plasma membrane in vicia guard cells are investigated using the whole-cell patch-clamp recording mode. It is shown that La³⁺ on both sides of plasma membrane blocks inward K⁺ currents in a concentration-dependent manner, indicating that La³⁺ binding sites may exist on both sides of plasma membrane in guard cells in vicia. The dose response is fitted by the Michaelis-Menten relation characterized by an inhibitor constant K _i of 2.56±0.25 μmol · L⁻¹ (outside membrane) and (1.18±0.11)×10⁻¹⁵ mol · L⁻¹ (inside membrane). Intracellular La³⁺ has much stronger inhibitory effect on inward K⁺ currents than extracellular La³⁺ does, suggesting there may exist stronger binding sites inside membrane than outside membrane. Since ion channel activities of guard cells directly affect plant stomatal movement and water status, our results imply that rare earth elements might have potential practical values in regulating plant water status and strengthening plant drought endurance.     

Structural role of large cations in sulfides with Cs<Superscript>+</Superscript> and Tl<Superscript>+</Superscript>

The results of a crystallographic analysis of the structures of CsFe₂S₃, Tl₂PbZrS₄, and Tl₂PbGeS₄ with a 1:1 cation–anion ratio are used to identify a joint F sublattice for Cs and S in the first compound and two separate F sublattices for cations and anions in the second compound (the PbS structural type). The substitution of the small Ge⁴⁺ (with its tetrahedral coordination by sulfur) for Zr⁴⁺ in the composition results in an increase in the unit cell volume, i.e., a decrease in the packing density for both cations and anions in the structure of the third compound. In the absence of regular F sublattices, there are “two-dimensional” orderings, typical of the PbS type, for the atomic positions in the projections of this structure.     

Hydration of the H<Superscript>+</Superscript>, Li<Superscript>+</Superscript>, Na<Superscript>+</Superscript>, and Cs<Superscript>+</Superscript> ions in MF-4SK perfluorinated sulfonic acid cation-exchange membranes modified with inorganic dopants

The hydration, state, and mobility of protons and Li⁺, Na⁺, and Cs⁺ ions in MF-4SK perfluorinated sulfonic acid cation-exchange membranes doped with silicon dioxide and phosphotungstic acid have been investigated by NMR and impedance spectroscopy. The dopants increase the moisture content of the membrane and change the system of pores and channels in which ion transport takes place. At low humidities, the dopant particles are involved in ion transport. The greatest effect is observed for the membranes doped with both SiO₂ and phosphotungstic acid. The water molecules sorbed by dopant particles as a material participate in the hydration of alkali metal cations in the membrane.     

Analysis of Li<Superscript>+</Superscript> cation migration paths in oxygen-containing compounds

Novel method for the studying of voids and channels in crystal structures is developed on the basis of the TOPOS structure-topology software. The method is using the Voronoi-Dirichlet crystal space partition. All ternary and quaternary lithium-containing inorganic compounds whose structure has been studied (822 compounds of the Li _a X _b O _z composition and 1349 compounds of the Li _a X1 _b X2 _c O _z composition, where X, X1, and X2 is any chemical element) are analyzed for the first time. The dimensionality of systems of the channels capable of transporting lithium ions is revealed. For all compounds, the migration patterns are constructed, which characterize systems of the conductance channels with the dimensionality 1, 2, and 3; the theoretically calculated coordinates of lithium atom positions in the voids’ centers agree well (accurate within 0.06 nm) with the known structure data. It is found, that 275 compounds have infinite channel system. Of this sampling, 249 compounds (125 structural types) have been described as solid electrolytes; the rest (26 compounds) can be thought of as potential ionic conductors with one-dimensional (6 types), two-dimensional (2 types), or three-dimensional (18 types) conductance.     

Structures of the nearest surroundings of the K<Superscript>+</Superscript>, Rb<Superscript>+</Superscript>, and Cs<Superscript>+</Superscript> ions in aqueous solutions of their salts

Published data on structural characteristics of hydration of K⁺, Rb⁺, and Cs⁺ ions in aqueous solutions of their salts under standard conditions, including authors’ X-ray diffraction data, are summarized and correlated. The structural parameters of the nearest surrounding of the K⁺, Rb⁺, and Cs⁺ ions, such as the coordination numbers, interparticle distances, and types of ionic association, are discussed. It is noted that, because of weak tendency of these cations to hydration, the parameters of their coordination spheres strongly depend on the concentration and chemical nature of counterions.     

Kinetics of solid-phase H<Superscript>+</Superscript>/M<Superscript>+</Superscript> ion exchange on hafnium hydrogen phosphate

The kinetics of solid-phase reactions between hafnium hydrogen phosphate and alkali metal chlorides were studied by thermogravimetry with subsequent analysis of leaving gases. For sodium and potassium chlorides, the reaction occurs in two stages; the first stages produces MHHf(PO₄)₂, and the second yields the MHf₂(PO₄)₃ NASICON phosphate. For rubidium chloride, the reaction is one stage and produces Rb₂Hf(PO₄)₂. For cesium chloride, the reaction is an analogue of the reaction for rubidium chloride, but has two stages. Kinetic data were used to determine interdiffusion coefficients for hydrogen and alkali-metal ions at various temperatures and the activation energies of interdiffusion.     

The solvation dynamics of Na<Superscript>+</Superscript> and K<Superscript>+</Superscript> ions in liquid methanol

The structure of the solvation shell of Na⁺ and K⁺ in fully deuterated liquid methanol has been studied by ab initio Car-Parrinello molecular dynamics simulations. The solvent cage has been found relatively stable and this property has been explained by means of charge transfer and electrostatic interactions as was previously done for Li⁺ in the same solvent. The differences with Li⁺ such as the increase of the coordination number going from Li⁺ to K⁺ and the reduced stability of the cage have been ascribed to the increase in the ionic radius.     

Selective ion-exchange sorption of K<Superscript>+</Superscript> from aqueous solutions containing Na<Superscript>+</Superscript>-K<Superscript>+</Superscript> mixture on Sn(IV) hydrophosphate

Ion-exchange sorption of K⁺ and Na⁺ from their mixture on X-ray-amorphous and crystalline Sn(IV) hydrophosphates was studied. These sorbents exhibit a high selectivity for K⁺. Amorphous Sn(IV) hydrophosphate can be used for efficient purification of aqueous sodium salt solutions to remove potassium impurity.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 8, 2004, pp. 1275–1278.Original Russian Text Copyright © 2004 by Smirnov, Dimova, Redchenko.     

A density functional theory study on the reactions of Y atom and Y+ cation with carbonyl sulfide

The mechanism of the title reactions have been studied by using the DFT (B3LYP/ECP/6‐311+G*) level of theory. Both ground and excited state potential energy surfaces are discussed. It is found the reaction mechanism is insertion mechanism both along the C? S and C? O bond activation branches, but the C? S bond activation is much more favorable in energy than the C? O bond activation. The reaction of Y atom with SCO was shown to occur preferentially on the ground state (doublet) PES throughout the reaction process, and the experimentally observed species, have been explained according to the mechanism revealed in this work. Different from that of Y + SCO system, the reaction between Y⁺ cation and SCO involves potential energy curve‐crossing which dramatically affects reaction mechanism. Due to the intersystem crossing existing in the reaction process of Y⁺ with SCO, the intermediates SY⁺(η²CO) and OY⁺(η²CS) may not form. All our theoretical results not only support the existing conclusions inferred from early experiment, but also complement the pathway and mechanism for this reaction. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Theoretical prediction on vibrational spectra of [Ar...Ar-H]<Superscript>+</Superscript>

Centrosymmetric linear [Ar-H-Ar]⁺ and asymmetric linear [Ar---Ar-H]⁺ are two stable configurations of [Ar₂H]⁺. Based on the global potential energy surface of [Ar₂H]⁺ provided by our group recently, we calculated the vibrational spectra of [Ar---Ar-H]⁺ with total angular momentum J = 0 by time-dependent quantum mechanical method, and the influence of quantum tunneling effect on vibrational spectra was found. With the help of the observation on the eigenstate functions and the modified potential energy surface, assignments were made to the spectra. The strong coupling between the excited bending mode of [Ar-H-Ar]⁺ and the vibrational states of [Ar---Ar-H]⁺ was discussed.     

Energetic ion bombardment of Ag surfaces by C<Stack><Subscript>60</Subscript><Superscript>+</Superscript></Stack> and Ga<Superscript>+</Superscript> projectiles

The ion bombardment-induced release of particles from a metal surface is investigated using energetic fullerene cluster ions as projectiles. The total sputter yield as well as partial yields of neutral and charged monomers and clusters leaving the surface are measured and compared with corresponding data obtained with atomic projectile ions of similar impact kinetic energy. It is found that all yields are enhanced by about one order of magnitude under bombardment with the C60+ cluster projectiles compared with Ga+ ions. In contrast, the electronic excitation processes determining the secondary ion formation probability are unaffected. The kinetic energy spectra of sputtered particles exhibit characteristic differences which reflect the largely different nature of the sputtering process for both types of projectiles. In particular, it is found that under C60+ impact (1) the energy spectrum of sputtered atoms peaks at significantly lower kinetic energies than for Ga+ bombardment and (2) the velocity spectra of monomers and dimers are virtually identical, a finding which is in pronounced contrast to all published data obtained for atomic projectiles. The experimental findings are in reasonable agreement with recent molecular dynamics simulations.     

Subcellular mass determination by <Superscript>4</Superscript>He<Superscript>+</Superscript> energy-loss micro-spectrometry

The scanning transmission ion microscope (STIM) has been used to determine the intracellular mass of human cultured cells. A 4He+ microbeam of 2.0 MeV energy was chosen to obtain enhanced ion-energy-loss sensitivity through the micron-thick freeze-dried cells. Local sample mass calculation, based on energy-loss conversion by use of appropriate matrix stopping powers, was performed by use of dedicated software. The method was validated with epoxy resin sections and polymer foil as analogues of biological samples in the range of (intra)cellular thickness, 150 to 3000 nm. STIM analysis resulted in less than 5% error in mass determination. 4He+ energy-loss micro-spectrometry was performed on freeze-dried human ovarian cancer cells, the mean areal mass obtained was 120 microg cm(-2) (200 microg cm(-2) in the nucleus and 250 microg cm(-2) in nucleoli). This method is particularly useful for mass normalization of X-ray fluorescence yields resulting from particle-induced X-ray emission microanalysis (micro-PIXE). When performed successively these two ion-beam micro-analytical methods enable the mapping of true element concentrations within single cells.     

Time-dependent inhibition of Na<Superscript>+</Superscript>/K<Superscript>+</Superscript>-ATPase induced by single and simultaneous exposure to lead and cadmium

Time-dependent interactions of Na⁺/K⁺-ATPase, isolated from rat brain synaptic plasma membranes (SPMs), with Cd²⁺ and Pb²⁺ ions in a single exposure and in a mixture were investigated in vitro. The interference of the enzyme with these metal ions was studied as a function of different protein concentrations and exposure time. The aim of the work was to investigate the possibility of selective recognition of Cd²⁺ and Pb²⁺ ions in a mixture, on the basis of the different rates of their protein-ligand interactions. Decreasing protein concentration increased the sensitivity of Na⁺/K⁺-ATPase toward both metals. The selectivity in protein-ligand interactions was obtained by variation of preincubation time (incubation before starting the enzymatic reaction). The text was submitted by the authors in English.