Hofmeister series and ionic effects of alkali metal ions on DNA conformation transition in normal and less polarised water solvent

Normal and less polarised water models are used as the solvent to investigate Hofmeister effects and alkali metal ionic effects on dodecamer d(CGCGAATTCGCG) B-DNA with atomic dynamics simulations. As normal water solvent is replaced by less polarised water, the Hofmeister series of alkali metal ions is changed from Li⁺ > Na⁺ ? K⁺ ? Cs⁺ ? Rb⁺ to Li⁺ > Na⁺ > K⁺ > Rb⁺ > Cs⁺. In less polarised water, DNA experiences the B→A conformational transition for the lighter alkali metal counterions (Li⁺, Na⁺ and K⁺). However, it keeps B form for the heavier ions (Rb⁺ and Cs⁺). We find that the underlying cause of the conformation transition for these alkali metal ions except K⁺ is the competition between water molecules and counterions coupling to the free oxygen atoms of the phosphate groups. For K⁺ ions, the ‘economics’ of phosphate hydration and ‘spine of hydration’ are both concerned with the DNA helixes changing.     

Effects of Li<Superscript>+</Superscript> co-doping on the concentration quenching threshold and luminescence of GdVO<Subscript>4</Subscript>:Eu<Superscript>3+</Superscript> nanophosphors

Europium ions (Eu³⁺) and Lithium ions (Li⁺) codoped gadolinium orthovanadate with a tetragonal phase had been successfully synthesized by an efficient hydrothermal method. X-ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence (PL) were utilized to characterize the microstructure, morphology, and luminescent properties of as-prepared samples. The various concentrations (0～14 at.%) of Li ions were applied to investigate the effect of Li⁺ co-doping concentration on the crystalline structure, microstructure, and emission intensity of GdVO₄:Eu³⁺, Li⁺ nanophosphors. The results demonstrated that Li⁺ ion co-doping changes the lattice parameters in two different ways. Moreover, the optical photoluminescent property was obtained when the Li⁺ co-doping concentration is 10 at.%. The influence of Li⁺ co-doping on the concentration quenching effect of Eu³⁺ was discussed as well. The concentration quenching threshold of Eu³⁺ was increased distinguishably. The potential mechanism was proposed in this paper.     

幻数尺寸Li-n-1,Lin,Li+ n+1(n=20,40)团簇的几何结构、电子与光学性质的第一性原理研究

基于密度泛函理论,采用第一性原理分子动力学模拟退火方法,对Li^-_n-1,Li_n,Li⁺_n+1 (n=20,40)的最低能量结构进行了全局搜索. 发现锂团簇的生长模式是以单个或多个嵌套的正多面体为核心,其余原子以五角锥为基本单元围绕核心生长. 基于最低能量结构的第一性原理电子结构计算得到锂团簇的分子轨道能级分布与无结构凝胶模型给出的电子壳层完全一致. 在总电 关键词： 团簇 电子结构 极化率 光吸收     

Lithium garnet oxide dispersed polymer composite membrane for rechargeable lithium batteries

Free-standing composite polymer membranes comprising of high molecular weight poly (ethylene oxide) (PEO) complexed with lithium perchlorate (LiClO₄) and Li₆La₂BaTa₂O₁₂ (LLBTO) garnet oxide as filler were developed via standard solution-casting method. The as-synthesized composite membranes were investigated through powder x-ray diffraction (PXRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and impedance spectroscopy techniques for their phase, thermal, morphological, and electrical properties, respectively. The lithium ion conductivity of polymer composite membranes consisting of PEO₈/LiClO₄ with various weight percents (5, 10, 15, 20, 25, and 30) of LLBTO were evaluated. We demonstrated a significant enhancement in Li⁺ conductivity with the addition of LLBTO to the polymer-lithium salt complex. Among the investigated membranes, the composite containing 20 LLBTO wt% garnet oxide exhibits maximized room temperature (30 °C) Li⁺ conductivity of 2.03 × 10^?4 S cm^?1 and electrochemical stability greater than 4.5 V.     

Lithium Distribution in Red Blood Cells and Plasma: NMR Studies of Rat Blood

To understand the interaction of lithium (Li⁺) with a coadministered drug in both the blood and the brain, we have treated rats with either Li⁺ alone or Li⁺ and a codrug. In this paper we address the important problem of quantitation of intra and extracellular Li⁺ ion contents in blood by the ⁷Li-NMR technique and the use of a shift reagent (SR). Although Li⁺ can be studied by atomic absorption techniques, these techniques involve tedious separation of intra- and extracellular components prior to chemical analysis. Magnetic resonance studies on rat blood, in the dose range of 0.5 to 10 meq/kg, indicate that the intracellular red blood cell Li⁺ predominates in the lower dose range of 0.5–1.0 meq/kg. As the lithium dose increases, a significantly larger amount of Li⁺ accumulates in the extracellular volume. Our studies on a number of animals at various doses of LiCl indicate that ⁷Li-NMR of blood samples provide a reliable, noninvasive quantification of red blood cell and plasma Li⁺ concentrations. The NMR method was further used to study the effect of coadministered drugs such as thioridazine on the intra- and extracellular Li⁺ concentration of RBCs.     

Correlation between Li+ adsorption capacity and the preparation conditions of spinel lithium manganese precursor

Spinel lithium manganese oxides can be used as Li⁺ adsorbent with topotactical extraction of lithium. In this paper, the solid state methods were introduced to prepare spinel lithium manganese precursors with Li₂CO₃ and LiOH·H₂O as different Li sources. The Li⁺ uptake was studied to clarify the correction between Li⁺ adsorption capacity and the preparation conditions of precursors, including different Li sources, Li/Mn mole ratios and heating time. The results indicated that the Li⁺-extracted materials prepared with LiOH·H₂O and MnCO₃ usually have higher Li⁺ adsorption capacity than Li₂CO₃ and MnCO₃, and an ascending trend was found in Li⁺ uptake with increasing Li/Mn mole ratio in the preparation of the precursor, but it is not proportional. The Mn₂O₃ impurities could be the primary reason for decreasing Li⁺ adsorption capacity. Furthermore, it is concluded that the Li⁺-extracted materials obtained from spinel manganese oxides synthesized with Li/Mn = 1.0 can serve as selective Li⁺ absorbents due to its high selectivity and large adsorption capacity.     

Bestimmung von Potentialparametern für die Wechselwirkung von Ionen und Atomen aus dem Beugungseffekt

This paper is concerned with the determination of the potential parameters from experimental results. The potential parameters are determined from the amplitudes and the positions of the experimental diffraction pattern by applying the general solution of the diffraction effect in [1]. All existing experimental results up to date are referred and evaluated. For the following scattering systems the potential parameters were determined and are presented in a table:⁷Li⁺-He,⁷Li⁺-Ne,⁷Li⁺-Ar,⁷Li⁺-Kr,⁷Li⁺-Xe,⁶Li⁺-Ar and H⁺- Ar.     

Cooperative Kinetics of Inhibition of Escherichia Coli Growth by Lithium Ions

In the present paper, a model of the cooperative kinetics of inhibition of Escherichia coli cell growth by Li⁺ ions is developed and experimentally tested. The interaction of various molecular targets for Li⁺ – transport proteins – in the biomass synthesis provides the basis for the model. An expression that describes the dependence of the specific cell growth rate on the Li⁺ ion concentration in the medium is derived and its adequacy is experimentally confirmed.     

Interaction of Li ions with ethylene carbonate (EC): Density functional theory calculations

Electronic structures of Li⁺ ion-ethylene carbonate (EC) complexes were studied by density functional theory. The structural, electronic and dynamical properties of Li⁺-EC complexes were studied for both an isolated EC molecule and clusters including Li⁺ ion. Our structural analysis showed only one type of Li⁺ coordination with EC through Li⁺?OC which was supported by the vibration spectral analysis for interaction between Li⁺ ion and a solvent (EC) molecule. It was analyzed that the solvation energy and Mulliken charge of Li+ ion solvated by EC molecule decrease with increase in number of EC molecule. However, electron affinity shows the opposite change. This analysis with solvation energy, electron affinity and Mulliken charge supported the stabilization of 4-coordinated solvation shell among [Li⁺(EC)_n]_n=1-5 complexes.     

Diffusion of Li ion on graphene: A DFT study

Density functional theory investigations show that the Li⁺ ion is stabilized at the center of hexagonal carbon ring with the distance of 1.84 Å from graphene surface. The potential barrier of Li⁺ ion diffusion on the graphene surface, about 0.32 eV, is much lower than that of Li⁺ ion penetrating the carbon ring which is 10.68 eV. When a vacancy of graphene exists, potential barrier about 10.25 eV for Li⁺ ion penetrating the defect is still high, and the ability of the vacancy to sizing the Li⁺ ion is also observed. Electronic densities of states show that the formation of a localized bond between Li atom and edge carbon of vacancy is the main reason for high potential barrier when Li⁺ ion penetrate a vacancy. While Coulomb repulsion is the control factor for high potential barrier in case of Li⁺ ion penetrating a carbon ring.     

Ionic and molecular Self-Diffusion in Ion-Exchange materials for fuel energetics studied by pulsed field gradient NMR

Pulsed field gradient nuclear magnetic resonance technique was applied to investigate the self-diffusion mechanism of water, alcohol molecules and Li⁻ counterions in sulfocation exchangers with different structures of the polymeric matrix. It was shown that in the homogeneous perfluorinated sulfocation exchange membranes the ionic and water translation motions are controled by the hydrogen bond network forming in ionogenic channels at the high water content. At the low solvent content, the self-diffusion coefficients of methanol and ethanol are higher than the water self-diffusion coefficients. The influence of non-ion-exchange sorbed electrolyte on Li⁺ self-diffusion coefficients was observed in the heterogeneous sulfocation exchanger KU-23.     

Characterization and application of radiation grafted membranes in waste treatment

Ionic membranes were prepared by radiation-induced grafting of acrylic acid onto low density polyethylene films. To elucidate the possibility of practical use, a study has been made for the characterization of the grafted and chemically treated membranes. The selectivity of such prepared membranes towards the chelation or complexation of different alkali metals was investigated, to find that the higher affinity is observed for K⁺, Na⁺ and Li⁺ ions compared to other alkali metals used. The metal uptake percent was determined using different techniques: flame photometer and X-ray fluorescence (XRF). The uptake of metal from its feed solution by the grafted membrane increased as the degree of grafting increased, i.e., it is directly proportional to the content of functional carboxylic acid groups in the graft copolymer. As a consequence, the electrical conductivity of metal feed solution decreased during such process of metal chelation by the membrane. The higher the grafting degree of membrane, the lower the electrical conductivity of metal feed solutions observed. The changes in thermal properties of the prepared membranes were investigated and characterized using differential scanning calorimeter (DSC), and thermal gravimetric analysis (TGA). The thermal stability of these membranes increased with a degree of grafting due to the formation of crosslinked network structure via hydrogen bonding. Furthermore, such stability is enhanced for the alkali-treated membranes even at high elevated temperatures. The prepared membranes showed a great promise for possible use in the recovery of uranium from zirconium in their wastes.     

冠醚对废旧锂离子电池浸出液中Li+选择性密度泛函理论研究

本文基于密度泛函理论研究了在水溶液中不同结构冠醚对Li~+的选择性.通过对几何结构、结合能和热力学的计算,发现15-冠-5(15C5)对Li~+的选择性强于12-冠-4(12C4)和18-冠-6(18C6).苯并15-冠-5(B15C5)与Li~+的结合能小于15C5,但在溶液巾结合Li~+时具有更低的自山能.研究了B15C5和Li、Co、Ni水合离子之间的交换反应,表明B15C5与水合锂离子之间的反应占据优势.上述结果表明采用B15C5从废旧钾离子电池浸出液中回收锂具有一定的可行性.     

Study of lithium adsorption on the TiO2 surface by electron-stimulated desorption

This paper reports on a study of electron-stimulated desorption (ESD) of O⁺ and Li⁺ ions from titanium dioxide as a function of the preheating temperature T and of the concentration of lithium adsorbed at 300 K, which was carried out with a static magnetic mass spectrometer combined with a retarding-field energy analyzer. For T>1500 K, the TiO₂ surface undergoes irreversible rearrangement. At temperatures from 300 to 900 K and at lithium coverages Θ<1, the ESD cross sections of the O⁺ and Li⁺ ions vary in a reversible manner with temperature, while for lithium coverages Θ>1, the changes in the Li⁺ and O⁺ ESD cross sections become irreversible. For θ<1, the appearance threshold of the Li⁺ and O⁺ ions is 25 eV, whereas for θ>1, the ESD threshold of Li⁺ ions shifts to 37 eV.     

Ab initio calculations of endo-and exohedral C60 fullerene complexes with Li+ ion and the endohedral C60 fullerene complex with Li2 dimer

The results of ab initio Hartree-Fock calculations of endo-and exohedral C₆₀ fullerene complexes with the Li⁺ ion and Li₂ dimer are presented. The coordination of the Li⁺ ion and the Li₂ dimer in the endohedral complexes and the coordination of Li⁺ ion in the exohedral complex of C₆₀ fullerene are determined by the geometry optimization using the 3–21G basis set. In the endohedral Li⁺C₆₀ complex, the Li⁺ ion is displaced from the center of the C₆₀ cage to the centers of carbon hexa-and pentagons by 0.12 nm. In the Li₂ dimer encapsulated inside the C₆₀ cage, the distance between the lithium atoms is 0.02 nm longer than that in the free molecule. The calculated total and partial one-electron densities of states of C₆₀ fullerene are in good agreement with the experimental photoelectron and X-ray emission spectra. Analysis of one-electron density of states of the endohedral Li⁺@C₆₀ complex indicates an ionic bonding between the Li atoms and the C₆₀ fullerene. In the Li⁺C₆₀ and Li⁺@C₆₀ complexes, there is a strong electrostatic interaction between the Li⁺ ion and the fullerene.     

Density functional theory calculations for ethylene carbonate-based binary electrolyte mixtures in lithium ion batteries

The density functional theory (DFT) calculations have been performed to investigate the interaction of Li⁺ with various organic solvents widely used as Li ion rechargeable battery electrolytes such as ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC); and their EC-based binary mixtures at the level of B3LYP/6-31G (d). The interaction of Li⁺ with these solvents has been calculated in terms of electronic structures of clusters of the mixtures of organic solvents including a lithium ion. The main objective of our investigation is to help in understanding a stable and enhancing ionic transfer at graphite/electrolyte interface assisted by the mixtures of the solvents. The calculated results favor the stability of EC-based binary mixtures and high EC-content binary mixture systems. In infrared (IR) vibrational spectra, the IR active modes of the solvent show significant changes due to the cation-solvent interaction.     

Reflectance spectrum of lithium hydride at the Li K-absorption edge

Reflectance spectra of LiH single crystals are measured at the Li⁺K- absorption edge for the first time. The ?₂ spectrum shows a prominent peak at 57.8 eV followed by several structures at the high energy side. We attribute the peak to a transition from the Li⁺ 1s to the n = 1 core exciton state associated with the p-like conduction band.     

Ionic conductivity of pure and doped Li3N

The ionic conductivity of Li₃N crystals doped with various metal ions (magnesium, copper and aluminum) or hydrogen has been investigated. The metal ions have a negative effect on the conductivity whereas hydrogen increases it. The intrinsic Li⁺ ionic conductivity of pure Li₃N is (2·-4)×10^-4Ω^-1cm^-1 at room temperature with an activation energy of 0.26?0.27 eV. Doping with hydrogen to a maximum level of 0.5?1.0 atom% results in a conductivity of 6×10^-3Ω^-1cm^-1 and an activation energy which has been lowered to 0.20 eV. A model is proposed for the action of hydrogen whereby the Li-N bonds next to an NH^2- group are weakened thereby facilatating the creation of Li⁺ Frenkel defects and the vacancy migration. Hydrogen-doped Li₃N is termed an enhanced intrinsic conductor.