X-ray diffraction and Raman spectra of merrillite at high pressures

ABSTRACT

The compressibility and effect of pressure on the vibrations of merrillite, Ca₉NaMg(PO₄)₇, were studied by using diamond anvil cell at room temperature combined with in-situ synchrotron X-ray diffraction and Raman spectroscopy up to about 18 and 15?GPa, respectively. The pressure-volume data was fitted by a third-order Birch–Murnaghan equation of state to determine the isothermal bulk modulus as K₀ ?=?87.2(32) GPa with pressure derivative K₀′?=?3.2(4). If K₀′?=?4, the isothermal bulk modulus was obtained as 81.6(10) GPa. The axial compressibility was estimated and an axial elastic anisotropy exists since a-axis is less compressible than the c-axis. The Raman frequencies of all observed modes for merrillite continuously increase with pressure, and the pressure dependences of stretching modes (v ₃ and v ₁) are larger than those of the bending modes (v ₄ and v ₂) and external modes. The isothermal mode Grüneisen parameters and intrinsic anharmonicity of merrillite were also calculated.     

Metastable states in high carbon C–(Fe,Ni, Co) films obtained by three-electrode ion-plasma sputtering

Abstract

The effect of ion-plasma deposition on the structure of high-carbon films (at. %) Fe–(20–84) % С, Co–(5–52) % С, Ni–(7–61) % С was investigated. The lattice periods and crystallite sizes of nonequilibrium phases in the as-deposited state and after heating are determined. The temperatures of the beginning and end of the decay of metastable phases during heating at a constant speed are established. The transition from an amorphous to an equilibrium crystalline state in Fe–C films passes through the stage of formation and subsequent decomposition of an intermediate, metastable hcp phase of variable composition. The electrical and hysteretic magnetic properties of the films were measured in the as-deposited state and after heat treatment. The compositions and conditions for producing films with low values of the temperature coefficient of electrical resistance and high coercive force are established. Thus, high-carbon films of Ni–61% C in the as-depoteted state and Fe–69% C films after heating to 900?K are characterized by small TCR values (± 10^?6 К^?1) over a wide temperature range.     

Developments of nano-polycrystalline diamond anvil cells for neutron diffraction experiments

ABSTRACT

A new high pressure cell for neutron diffraction experiments using nano-polycrystalline anvils is presented. The cell design, off-line pressure generation tests and a gas-loading procedure for this cell are described. The performance is illustrated by powder neutron diffraction patterns of ice VII to ～82?GPa. We also demonstrate the feasibility of single crystal neutron diffraction experiments of Fe₃O₄ at ambient conditions using this cell and discuss the current limitation and future developments.     

A Zinc(II) Photocage Based on a Decarboxylation Metal Ion Release Mechanism for Investigating Homeostasis and Biological Signaling

Metal ion signaling in biology has been studied extensively with ortho‐nitrobenzyl photocages; however, the low quantum yields and other optical properties are not ideal for these applications. We describe the synthesis and characterization of NTAdeCage, the first member in a new class of Zn²⁺ photocages that utilizes a light‐driven decarboxylation reaction in the metal ion release mechanism. NTAdeCage binds Zn²⁺ with sub‐pM affinity using a modified nitrilotriacetate chelator and exhibits an almost 6 order of magnitude decrease in metal binding affinity upon uncaging. In contrast to other metal ion photocages, NTAdeCage and the corresponding Zn²⁺ complex undergo efficient photolysis with quantum yields approaching 30 %. The ability of NTAdeCage to mediate the uptake of ⁶⁵Zn²⁺ by Xenopus laevis oocytes expressing hZIP4 demonstrates the viability of this photocaging strategy to execute biological assays.     

Crystal Structure of Cesium Phenylacetylide,CsC2C6H5, Solved and Refined from Synchrotron Powder Diffraction Data

The crystal structure of cesium phenylacetylide, CsC₂C₆H₅, was solved and refined from synchrotron powder diffraction data (Pbca, Z = 8). Each Cs⁺ cation is coordinated by five ligands: four acetylide groups coordinate side‐on and one end‐on. A similar arrangement is found in the crystal structure of NaC₂H (P4/nmm, Z = 2). There is a group‐subgroup relationship between both structures. Most importantly, the crystal structure of CsC₂C₆H₅ could only be solved with the help of synchrotron data, as the very good peak:noise ratio allowed the assignment of several very weak reflections, which finally led to the correct space group, in which a structural solution was possible using direct space methods.     

Soluble Congeners of Prior Insoluble Shape-Persistent Imine Cages

One of the most applied reaction types to synthesize shape-persistent organic cage compounds is the imine condensation reaction and it is assumed that the formed cages are thermodynamically controlled products due to the reversibility of the imine condensation. However, most of the synthesized imine cages reported are formed as precipitate from the reaction mixture and therefore rather may be kinetically controlled products. There are even examples in literature, where resulting cages are not soluble at all in common organic solvents to characterize or study their formation by NMR spectroscopy in solution. Here, a triptycene triamine containing three solubilizing n-hexyloxy chains has been used to synthesize soluble congeners of prior insoluble cages. This allowed us to study the formation as well as the reversibility of cage formation in solution by investigating exchange of building blocks between the cages and deuterated derivatives thereof.     

Synthesis,Spectral, X‐Ray Diffraction,DFT, and Nematicidal Activity of Mixed Ligand Complexes of Ethyl 2‐(2‐Hydroxybenzylidine)‐Hydrazine Carboxylate and 1,10‐Phenanthroline with Some Transition Metals

In this work, mixed ligand complexes derived from ethyl 2‐(2‐hydroxybenzylidine)‐hydrazine carboxylate (HL) and 1,10‐phenanthroline (Phen) as ligands were synthesized and their structures elucidated by elemental analysis, infrared (IR), electronic,¹H NMR, and mass spectra, X‐ray diffraction (XRD), magnetic susceptibility measurements, and TG/DTG analyses. The analytical and spectral data support the formation of the complexes with the central ion in each complex six‐coordinated and a slightly distorted octahedral geometry. The IR spectra showed that HL and Phen ligands act as neutral bidentates. The XRD patterns of the complexes showed their crystalline nature. The calculated bond length and the force constant F (U═O) in the uranyl complex are 1.738 Å and 685.90 Nm⁻¹, respectively. The molar conductance values of the synthetic complexes in DMF were found to be in the range 5.00–274.06 S cm²/mol at room temperature. The thermodynamic parameters were evaluated by using the Coats–Redfern (CR) and Horowitz–Metzeger (HM) methods. Theoretical molecular structures were investigated by the density functional theory/B3LYP method using the Gaussian 98 W basis set. The nematicidal activity of the ligands and its metal complexes was also studied.     

A new 3D supramolecular Zn(II) compound: Crystal structure and important role in treatment of pulpitis

An innovative thermostable 2-D layered Zn(II) compound, chemical terms are written as [Zn(3-pysa)₂(H₂O)₂]_n (1, 3-Hpysa = 3-pyridinesulfonic acid), has been generated from the solvothermal reactions of 3-Hpysa and Zn(NO₃)₂·6H₂O. Its single crystal analysis was implemented via the single crystal X-ray diffraction analysis together with the powder X-ray diffraction, elemental analysis and thermogravimetric analysis. The crystal framework is of monoclinic P2₁/n space group and its crystal cell figures: a = 7.7499(5), b = 10.9923(6), c = 8.3430(5) Å, α = 90, β = 96.924(6), γ = 90°, V = 705.55(7) ų, Z = 4. The 2D layers were finally combined to a 3-D supramolecular conformation through intermolecular H-bonds existing between coordinated H₂O molecules and sulfonate oxygen atoms from adjacent layer. Its practical role in pulpitis treatment was estimated and the relevant mechanism was studied in the meantime.     

Plane strain wave in an isotropic layer of a viscoelastic material

The velocity and the rate of decay of a strain wave in a layer of a viscoelastic material rigidly fixed on a solid foundation are determined. The wave structure (ratio of the longitudinal to the transverse displacement) and the profiles of these displacements are analyzed. Attenuation of waves in the first mode is found to be more significant than that in an infinite space. The most intense decay is observed at resonance frequencies. A strong effect of compressibility of the medium on wave parameters is revealed. Conditions at which such a system operates as a waveguide are found. For a loss tangent higher than 0.13 (for an incompressible medium), the character of the dispersion dependence is observed to change drastically: the wave velocity decreases with decreasing frequency. __________ Translated from Prikladnaya Mekhanika i Tekhnicheskaya Fizika, Vol. 47, No. 3, pp. 104–111, May–June, 2006.