EPR spectra of Mn2+ ions in precipitated divalent impurity phases in monocrystalline NaCl

The EPR spectra of Mn²⁺ ions embedded into precipitated phases of Mg²⁺, Cd²⁺, Fe²⁺ and Ca²⁺ in NaCl single crystals have been investigated. The spectrum from samples whose major impurity is Mg, Cd or Fe corresponds to Mn²⁺ substituting some divalent cation inside the Suzuki phase (6NaCl.MCl₂). The existence of such a phase has been ascertained by means of Raman spectroscopy. On the other hand, the EPR spectrum of Ca²⁺ doped samples has been attributed to Mn²⁺ inside various CaCl₂ precipitates.     

Nuclear Magnetic Ions of Magnesium,Calcium, and Zinc as a Powerful and Universal Means for Killing Cancer Cells

Magnetic isotope effect controls enzymatic DNA synthesis and strongly, by 2–3 times, suppresses catalytic activity of polymerases and increases even more strongly, by 20–50 times, the mortality of cancer cells. Catalyzing ions ²⁵Mg²⁺, ⁴³Ca²⁺, and ⁶⁷Zn²⁺ carrying magnetic nuclei are shown to efficiently kill cancer cells. The advantage of these ions for practical medicine is that being injected in blood they are captured selectively and almost exclusively by cancer cells inducing their death. The healthy cells capture these ions much less efficiently (perhaps due to the lower penetrability of their membranes) and are not vulnerable to these ions in comparison with cancer cells. Of course, penetrability of cells is identical for magnetic and nonmagnetic ions, but only the former kill cancer cells.     

The influence of thermal processing on the relative mobility of edge and screw dislocations in NaCl crystals

The effect of thermal processing on the mobility of dislocations is investigated in NaCl crystals doped with impurities of various types—high-solubility impurities (Ca²⁺) and low-solubility impurities (Pb²⁺). The results obtained after aging and thermal processing indicate that the type of impurity and its state (e.g., level of aggregation) in the crystal have a strong effect on the relative mobility of edge and screw dislocations, and also on the parameters of double transverse slip. Fiz. Tverd. Tela (St. Petersburg) 41, 1041–1043 (June 1999)     

Crystal structure and luminescence properties of Lu3+ and Mg2+ incorporated silicate garnet [Ca3−(x+0.06)LuxCe0.06](Sc2−yMgy)Si3O12

The yellow-emitting phosphor [Ca_3?(x+0.06)Lu_xCe_0.06](Sc_2?yMg_y)Si₃O₁₂ obtained from Lu³⁺ and Mg²⁺ co-modified green-emitting silicate garnet Ca₃Sc₂Si₃O₁₂:Ce³⁺ (CSS:Ce³⁺) exhibits promising applications for white LEDs. In this paper, we discuss the effect of charge balance on the garnet structure formation. The changes of bond length and covalence caused by the replacement of Lu³⁺ and Mg²⁺ for Ca²⁺ and Sc³⁺ are analyzed. The shift of the Ce³⁺ emission and excitation can be attributed to the combined results from crystal field splitting effect and centroid shift of Ce³⁺ 5d levels. Thermal stability is analyzed according to configurational coordinate diagram.     

Influence of crystallographic orientation of biogenic calcite on in situ Mg XANES analyses

Micro X‐ray absorption near‐edge spectroscopy at the Mg K‐edge is a useful technique for acquiring information about the environment of Mg²⁺ in biogenic calcite. These analyses can be applied to shell powders or intact shell structures. The advantage of the latter is that the XANES analyses can be applied to specific areas, at high (e.g. micrometre) spatial resolution, to determine the environment of Mg²⁺ in a biomineral context. Such in situ synchrotron analysis has to take into account the potential effect of crystallographic orientation given the anisotropy of calcite crystals and the polarized nature of X‐rays. Brachiopod shells of species with different crystallographic orientations are used to assess this crystallographic effect on in situ synchrotron measurements at the Mg K‐edge. Results show that, owing to the anisotropy of calcite, in situ X‐ray absorption spectra (XAS) are influenced by the crystallographic orientation of calcite crystals with a subsequent potentially erroneous interpretation of Mg²⁺ data. Thus, this study demonstrates the importance of crystallography for XAS analyses and, therefore, the necessity to obtain crystallographic information at high spatial resolution prior to spectroscopic analysis.     

Influence of divalent cationic impurities on plasticity of AgCl

The hardening effect of Mg²⁺, Ca²⁺, Sr²⁺, Cd²⁺ and Ba²⁺ impurities in polycrystalline AgCl was investigated. With exception of Mg²⁺ the hardening effect of the impurities decreases with increasing atomic number (atomic weight). The hardening effects of Mg²⁺ and Ca²⁺ are expressively stronger than those of the three remaining impurities. Approximately linear dependence of the stress at the beginning of plastic deformation on the impurity concentration was found. Possible causes of the different hardening effects of the divalent impurities are discussed.     

Hydration characteristics of Ca2+ and Mg2+: a density functional theory,polarized continuum model and molecular dynamics investigation

In this work, density functional theory, Møller–Plesset second-order perturbation theory, and ab initio molecular dynamics (AIMD) were used to investigate hydrated characteristics of Mg²⁺ and Ca²⁺ as a function of coordination number in the first hydration shell (CN) and cluster size. It is generally accepted that the CNs of Mg²⁺ and Ca²⁺ are both six. Calculations show that the hydration of Mg²⁺ generally prefers six-coordinated structures, whereas the CN value of Ca²⁺ varies from 6 to 8 as the hydration proceeds. Moreover, the first hydration of Ca²⁺ is found to be more flexible than that of Mg²⁺, as indicated by the results of transition state calculations and AIMD simulations. In addition, the constraint of Mg²⁺ on the first hydration shell is obviously stronger than that of Ca²⁺, while the constraint on the inner hydration shells fades slightly faster for Mg²⁺ than Ca²⁺. It is also found that the charge transfer from central cation to water molecules is affected only by the first hydration shell for Mg²⁺, whereas by the first and second hydration shells for Ca²⁺. Based on hydration characteristics, approximatively saturated ion hydration shells for the hydration of Mg²⁺ and Ca²⁺ were proposed.     

Calcifications in human osteoarthritic articular cartilage: ex vivo assessment of calcium compounds using XANES spectroscopy

Calcium (Ca²⁺)‐containing crystals (CCs), including basic Ca²⁺ phosphate (BCP) and Ca²⁺ pyrophosphate dihydrate (CPPD) crystals, are associated with severe forms of osteoarthritis (OA). Growing evidence supports a role for abnormal articular cartilage mineralization in the pathogenesis of OA. However, the role of Ca²⁺ compounds in this mineralization process remains poorly understood. Six patients, who underwent total knee joint replacement for primary OA, have been considered in this study. Cartilage from femoral condyles and tibial plateaus in the medial and lateral compartments was collected as 1 mm‐thick slices cut tangentially to the articular surface. First, CCs presence and biochemical composition were assessed using Fourier transform infrared spectroscopy (FT‐IR). Next, Ca²⁺ compound biochemical form was further assessed using X‐ray absorption spectroscopy (XAS) performed at the Ca²⁺K‐absorption edge. Overall, 12 cartilage samples were assessed. Using FT‐IR, BCP and CPPD crystals were detected in four and three out of 12 samples, respectively. Ca²⁺ compound biochemical forms differed between areas with versus without CCs, when compared using XAS. The complete set of data shows that XANES spectroscopy can be used to accurately characterize sparse CCs in human OA cartilage. It is found that Ca²⁺ compounds differ between calcified and non‐calcified cartilage areas. In calcified areas they appear to be mainly involved in calcifications, namely Ca²⁺ crystals.     

CRYSTAL STRUCTURE AND MAGNETIC PROPERTIES OF La1.2Sr1.8-xCaxMn2O7

The effect of divalent cation substitution on the structure and magnetic properties of La_1.2Sr_1.8-xCa_xMn₂O₇ (x = 0－0.900) is investigated in this paper. Partly replacing divalent cation Sr²⁺ by Ca²⁺ ions results in the weakening and then disappearance of long-range ferromagnetic ordering, and the formation of spin canting and low-temperature spin-glass. Based on structural analysis by Rietveld profile fitting, we suggest that this variation of magnetic property be related to a Jahn－Teller-type attice distortion of MnO₆ octahedra due to the introduction of the smaller sized Ca²⁺ ions.     

Specific Mg binding to AT-rich regions of chromatin in the evolution of eukaryotes

At SIMS XIV, we reported SIMS evidence of specific Mg²⁺ binding to the AT-rich regions of human metaphase chromosomes represented by G-bands. Subsequent Mg²⁺-depletion experiments supported a direct role for Mg²⁺ in promoting and maintaining the higher order chromatin structure originating G-bands, possibly due to both Mg²⁺-DNA and Mg²⁺-protein interactions. An in-depth study, reported elsewhere, implicated also Ca²⁺ in the maintenance of chromatin ultrastructure in the scaffold of mammalian chromosomes, in association with topoisomerase II.We examine here the association of Mg²⁺ with AT-rich regions of chromatin in the chromosomes of the Indian muntjac deer (IMD), leading to conclusions similar to the above. To answer the question whether the presumed divalent cation role in the chromosomes of advanced eukaryotes had an evolutionary history to be traced back to earlier evolutionary stages, we have SIMS-mapped Ca²⁺ and Mg²⁺ in BrdU-labeled polytene chromosomes from the salivary gland of the Dipteran Drosophila melanogaster. Striking Ca²⁺ and Mg²⁺ SIMS banding patterns correlating with those of the Br label (a thymidine analogue) implicate unequivocally a close association of both these cations with the AT-rich regions of DNA for these primitive eukaryotes.     

Manifestation of a Photorefractive Effect in the Raman Scattering Spectra of Lithium Niobate Crystals of Variable Composition

Using the Raman scattering spectra, we investigated the ordering of the structural units in the cation sublattice and the photorefractive properties of lithium niobate single crystals of variable composition, i.e., nominally pure ones with different Li/Nb ratios and those doped with the nonphotorefractive cations Mg²⁺, Gd³⁺, and Y³⁺. It is shown that at low concentrations of Mg²⁺, Gd³⁺, and Y³⁺ the magnitude of the photorefractive effect is substantially determined by the ordering of the structural units of the cation sublattice. It has been found for the first time that the intensity of the line corresponding to the bridge valence vibrations of oxygen atoms in the octahedrons of NbO₆ is sensitive to the dipole ordering of the cation sublattice of the crystal. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 5, pp. 611–614, September–October, 2005.     

Photocontrolled magnetic resonance plasticity of γ-irradiated KCl:Fe crystals

A photocontrolled resonance decrease in microhardness, which is due to the application of mutually perpendicular static and microwave fields, in γ-irradiated KCl:Fe crystals has been revealed. It has been found that the magnetic plasticity of unirradiated γ-KCl:Fe crystals is due to the resonance effect of magnetic fields on two types of impurity centers: first, centers containing Fe²⁺-ν _c ion-vacancy pairs and, second, centers containing Fe⁺ ions. The illumination of γ-KCl:Fe crystals with F-light (with a wavelength of λ = 500–600 nm) is accompanied by rearrangement of the spectrum of electron paramagnetic resonance detected by a change in microhardness. The effect of F-light on the spectrum of magnetic resonance plasticity is manifested as the suppression of the spectra of Fe²⁺-ν _c ions with effective g-factors of 7.0 and 3.5 due to their recombination with F-electrons and reconstruction to Fe⁺ centers with g-factors of 2.2 and 4.1.     

Studies on adsorptions of metallic ions in water by zirconium glyphosate (ZrGP): Behaviors and mechanisms

A new adsorbent named zirconium glyphosate [Zr(O₃PCH₂NHCH₂COOH)₂·0.5H₂O, denoted as ZrGP] and its selective adsorptions to Pb²⁺, Cd²⁺, Mg²⁺ and Ca²⁺ ions in water were reported in this paper. Compared to other zirconium adsorbents, such as zirconium phosphate [Zr(HPO₄)₂], ZrGP exhibited highly selective adsorption to Pb²⁺ in solution which contained Pb²⁺, Cd²⁺, Mg²⁺ and Ca²⁺ ions. The loaded ZrGP with metallic ions can be efficaciously regenerated by aqueous solution of HCl (1.0 M) without any noticeable capacity loss, and almost all of it can be reused and recycled. The memory effect on structural regeneration of ZrGP was also found when Mg²⁺ and Ca²⁺ were adsorbed. To be specific, the structure of ZrGP was destroyed due to adsorbing these two ions, but it could be regenerated after the loaded materials were dipped in HCl solution (1.0 M) for several minutes to remove metallic ions.     

Preparation,characterization, and ion exchange behavior of nanocomposite polyaniline zirconium(IV) selenotungstophosphate for the separation of toxic metal ions

A conducting polymer-based advanced nanocomposite ion exchanger was synthesized by incorporating polyaniline (PANI) into the inorganic counterpart zirconium(IV) selenotungstophosphate (ZSWP). The nanocomposite exhibited an excellent ion exchange capacity of 1.20 meq g^?1 in addition to high thermal stability. The polymeric–inorganic nanocomposite ion exchanger was characterized by Fourier transform infrared (FTIR), XRD, SEM, and TEM studies. The DC conductivity of PANI/ZSWP was also investigated. The nanocomposite ion exchanger was found to be highly selective for Cu²⁺ ions with a distribution coefficient value of 650 mL/g. The analytical applications of the material were explored by achieving selective separations of Cu²⁺ and Ca²⁺ ions from a synthetic mixture of Cu²⁺, Pb²⁺, Zn²⁺, Ni²⁺, Fe³⁺, Mg²⁺, and Al³⁺ and Ca²⁺, Pb²⁺, Zn²⁺, Ni²⁺, Al³⁺, Mg²⁺, and Ba²⁺.     

Residues at the tip of the pore loop of NR3B-containing NMDA receptors determine Ca<Superscript>2+</Superscript> permeability and Mg<Superscript>2+</Superscript>block

Background  

Members of the complex N-methyl-D-aspartate receptor (NMDAR) subfamily of ionotropic glutamate receptors (iGluRs) conventionally assemble from NR1 and NR2 subunits, the composition of which determines receptor properties. Hallmark features of conventional NMDARs include the requirement for a coagonist, voltage-dependent block by Mg²⁺, and high permeability for Ca²⁺. Both Mg²⁺ sensitivity and Ca²⁺ permeability are critically dependent on the amino acids at the N and N+1 positions of NR1 and NR2. The recently discovered NR3 subunits feature an unprecedented glycine-arginine combination at those critical sites within the pore. Diheteromers assembled from NR1 and NR3 are not blocked by Mg²⁺ and are not permeable for Ca²⁺.     

Electric stimulation of magnetoplasticity and magnetic hardening in crystals

The effect of electric field E on the magnetoplastic effect (MPE) has been investigated in NaCl crystals with different impurities, which provide either the plasticization of the samples in the magnetic field (positive MPE) or their magnetic hardening (negative MPE). The mobility of individual dislocations under the joint action of the magnetic and electric fields and the mechanical load on the crystals has been studied. The sharp electric stimulation of the MPE of both signs has been revealed, i.e., an increase or a decrease in the mean free path of dislocations that is roughly proportional to exp(±E/E ₀) at E ? E ₀ ～ 1–10 kV/m. In particular, in the negative-MPE NaCl(Pb) crystals, the accompanying electric field enhances the magnetic suppression of plasticity. The results are attributed to the electrically induced transformation of the additional part of the pinning impurity ions Me⁺⁺ to the magnetically active state of Me⁺ on the dislocations. The subsequent magnetic transformation of the structure of these pinning centers should lead to a sharper variation of the dislocation pinning force (either an increase or a decrease, depending on the MPE sign).     

Multifrequency EPR spectroscopy of Ho3+ ions in synthetic forsterite

Electron paramagnetic resonance (EPR) of Ho³⁺ single ions and Ho³⁺?Mg²⁺-vacancy-Ho³⁺ associates in holmium-doped forsterite single crystals are studied at 9.4, 37.3 and 65–250 GHz. Crystals were grown from melt by the Czochralski technique in slightly oxidizing atmosphere. For both centers, directions of the principal magnetic axes and parameters of the effective spin Hamiltonians describing dependences of electron-nuclear levels on applied magnetic field are obtained. For Ho³⁺ substituting Mg²⁺ in the M2 site as the single ion and for Ho³⁺ ions in dimer centers, values of crystal field parameters related to a real crystal lattice structure are estimated in the framework of the exchange charge model. The calculated crystal field energies, values of theg-factors of the ground Ho³⁺ quasi-doublet and the directions of the corresponding magnetic moments agree satisfactorily with the data obtained from measurements of EPR and optical absorption and site-selective luminescence spectra.     

New aspects on the dielectric properties of the alkali halides with divalent impurities

Dielectric losses were measured in the following crystals NaCl+ (Mg²⁺, Co²⁺, Ni²⁺, Sr²⁺, Ca²⁺, Mn²⁺, Zn²⁺, Cd²⁺, Ba²⁺, Pb²⁺), KCl + (Ca²⁺, Sr²⁺, Ba²⁺, ²⁺, Pb²⁺) and KBr + (Sr²⁺, Ba²⁺) in the frequency region 5–500 kHz. It was found that when the divalent cation impurity has an electronic configuration similar to the inert gases (1) no observable deviation from simple Debye theory exists (2) the activation energy Φ increases linearly with the ionic radius of the impurity.The above observations (1) and (2) do not hold when the divalent cation impurity has d-electrons in the outer subshell.     

73Ge NMR spectra in germanium single crystals with different isotopic composition

We have studied the influence of isotopic disorder on the local deformations in Ge single crystals from both experimental and calculation points of view. The nuclear magnetic resonance (NMR) spectra of⁷³Ge nuclei (the nuclear spin equals 9/2) in perfect single crystals of germanium with different isotopic content were measured at temperatures 80, 300 and 450 K. Abnormal broadening of the spectrum was found to occur when the magnetic field was aligned along the [111] axis of a crystal. The observed specific angular dependence of the quadrupole broadening was attributed to isotopic disorder among atoms of germanium sited around the⁷³Ge NMR probe. Local lattice deformations in germanium crystal lattice due to isotopic impurity atoms were calculated in the framework of the adiabatic bond charge model. The results obtained were applied to study random noncubic crystal field interactions with the nuclear quadrupole moments and corresponding effects in NMR spectra. Simulated second and fourth moments of resonance frequency distributions caused by the magnetic dipole-dipole and electric quadrupole interactions are used to analyze the lineshapes, theoretical predictions agree qualitatively with the experimental data.     

Electrochemical luminescence of Mg1−xCaxIn2O4:Er electrodes

Improvement for electrochemical luminescence (ECL) property of MgIn₂O₄ is attempted by partial exchange of Mg²⁺ ion in MgIn₂O₄ to Ca²⁺ ion. Mg_1−xCa_xIn₂O₄ solid solution was obtained in the region 0<x<0.4. Efficiency for ECL per unit current for Mg_1−xCa_xIn₂O₄:Er³⁺ increased with the increase in the ratio of Ca²⁺ ion, and showed a peak at x=0.25 and then decreased steeply. ECL efficiency for other rare-earth ion-(RE:Sm, Eu, Ho) doped Mg_1−xCa_xIn₂O₄ also increased comparing with those for MgIn₂O₄:RE. This Ca²⁺ addition effect on the ECL efficiency seems to be caused by the improvement of the efficiency for the impact activation.