Rhenium alkoxides

The data on synthesis of individual and heterometallic alkoxide and oxoalkoxide derivatives of rhenium are summarized. Their structures are considered, characteristic features and peculiarities of the structures are analyzed. Data on the thermal decomposition of rhenium alkoxides and its application for the preparation of rhenium-based metallic and oxide materials are given. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2177–2188, October, 2005.     

An YBCO film as a Josephson medium near T c : Frequency and field dependences and scaling relationships

The diamagnetic response of a laser-deposited YBCO film was studied in weak exciting magnetic fields H _ac =H ₀sinωt (H ₀=2–500 mOe, ω/2π=1–30 kHz). An analysis of the experimentally measured diamagnetic response showed evidence of a ring character of the electric field flowing in the sample at small H ₀ values. The plots of T _m (the temperature of maximum dissipative losses χ″₁) versus H ₀ measured at various frequencies showed the existence of a certain critical field strength H*(ω) at which the (1?T _m /T _c ) versus H ₀ ^2/3 plots exhibit a break. A logarithmic dependence of T _m on the frequency ω of the exciting field H _ac is reliably valid only in the region of (ω/2π)>5 kHz. Verification of the scaling relationship showed that this relationship is valid (to within the experimental accuracy) for the frequencies ω above 5 kHz and the field amplitudes H ₀>H*(ω). However, the exponent n in the scaling relationship under consideration is not correlated with the exponent n in the power relationship describing the current-voltage characteristic.     

Heterogeneous equilibria in the rhenium-oxygen system

The heterogeneous phase equilibria in the rhenium-oxygen system (over a composition range of Re₂O₇-Re) were studied using differential thermal analysis, x-ray diffraction analysis, and tensimetry. The system was found to contain the equilibrium phases of Re₂O₇, cubic ReO₃, and orthorhombic ReO₂. A region of homogeneity of orthorhombic ReO₂ was hypothesized to exist. Monoclinic ReO_2+x was demonstrated to be metastable. The p-T and T-x projections of the phase diagram of the system were constructed.     

Silicon oscillistor as a thermometer with frequency output

We present experimental results for a silicon thermometer (p⁺-p-n⁺ device placed between the poles of a permanent magnet) with a frequency output. Measurements were made for temperatures in the range 77–335 K. When the temperature increases from 77 K to 335 K the device sensitivity decreases from 40 kHz/K to 3.1 kHz/K for a pulsed operating voltage of 65 V. The device sensitivity can be controlled through the operating voltage. We analyze the basic properties of thermometer element using the theory of the bulk helical instability of the semiconductor plasma. We compare its performance parameters with those of previously known devices with frequency outputs.V. D. Kuznetsov Siberian Physico-technical Institute at Tomsk University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 48–53, February, 1995.     

Mn site substitution of La0.67Ca0.33MnO3 with closed shell ions: Effect on magnetic transition temperature

Mn site is substituted with closed shell ions (Al, Ga, Ti, Zr and a certain combination of Zr and Al) and also with Fe and Ru ions carrying the magnetic moment (S=5/2 and 2 respectively) at a fixed concentration of 5 at %. Substitution did not change either the crystal symmetry or the oxygen stoichiometry. All substituents were found to suppress both the metal-insulator and ferromagnetic transition temperatures (T _p(ρ) and T _C, respectively) to varied extents. Two main contributions identified for the suppression are the lattice disorder arising due to difference in the ionic radii between the substituent (r _M) and the Mn³⁺ ion (r _Mn ³⁺) and in the case of the substituents carrying a magnetic moment, the type of magnetic coupling between the substituent and that of the neighboring Mn ion.     

Kink instability of the semiconductor plasma in silicon parallelepipeds

Experimental results on the onset of the kink instability of the semiconductor plasma in silicon p⁺-p-n⁺ structures are analyzed. The structures were parallelepipeds. The experiments were carried out over the temperature range from 77 to 300 K. The shape of the current-voltage characteristics and that of the threshold curves of the test samples are discussed. The frequency and amplitude of the alternating current which arises as a result of the kink instability are described as a function of the electric field and the magnetic induction at levels substantially above the excitation threshold.V. D. Kuznetsov Siberian Physicotechnical Institute, Tomsk State University. Scientific-Research Institute of Semiconductor Devices. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 5, pp. 103–110, May, 1992.     

Electrochemical synthesis, structural characterization, and decomposition of rhenium oxoethoxide, Re4O4(OEt)12. Ligand influence on the structure and bonding in the high-valent tetranuclear planar rhenium alkoxide clusters

Anodic oxidation of rhenium in ethanol in the presence of LiCl as a conductive additive results with high yield in formation of a new oxoethoxide cluster, Re(4)O(4)(OEt)(12). The structure of the planar centrosymmetric metal-oxygen core of this molecule is composed of four edge-sharing Re(V)O(6) octahedra. Eight electrons are available for the formation of metal-metal bonds indicated by five relatively short Re-Re distances within the Re 4-rhombus, a "planar butterfly" type cluster. The theoretical calculations are indicating relatively low contribution of metal-metal bonding in the stability of the core. The stability of the +V-oxidation state, unusual for rhenium alkoxides can be at least partially attributed to the size effects in the packing of ligands. The X-ray powder study indicates that treatment of Re(4)O(4)(OEt)(12). in ambient atmosphere rapidly transforms it into a mixed-valence derivative Re(4)O(6)(OEt)(10) with a structure related to the earlier investigated cluster Re(4)O(6)(O(i)Pr)(10). Thermal decomposition of the latter rhenium oxoethoxide results in reduction to rhenium metal at as low temperatures as 380 degrees C, producing aggregates of metal nanoparticles with the average size of 3 nm.     

Americium preferred: lanmodulin,a natural lanthanide-binding protein favors an actinide over lanthanides

The separation and recycling of lanthanides is an active area of research with a growing demand that calls for more environmentally friendly lanthanide sources. Likewise, the efficient and industrial separation of lanthanides from the minor actinides (Np, Am–Fm) is one of the key questions for closing the nuclear fuel cycle; reducing costs and increasing safety. With the advent of the field of lanthanide-dependent bacterial metabolism, bio-inspired applications are in reach. Here, we utilize the natural lanthanide chelator lanmodulin and the luminescent probes Eu³⁺ and Cm³⁺ to investigate the inter-metal competition behavior of all lanthanides (except Pm) and the major actinide plutonium as well as three minor actinides neptunium, americium and curium to lanmodulin. Using time-resolved laser-induced fluorescence spectroscopy we show that lanmodulin has the highest relative binding affinity to Nd³⁺ and Eu³⁺ among the lanthanide series. When equimolar mixtures of Cm³⁺ and Am³⁺ are added to lanmodulin, lanmodulin preferentially binds to Am³⁺ over Cm³⁺ whilst Nd³⁺ and Cm³⁺ bind with similar relative affinity. The results presented show that a natural lanthanide-binding protein can bind a major and various minor actinides with high relative affinity, paving the way to bio-inspired separation applications. In addition, an easy and versatile method was developed, using the fluorescence properties of only two elements, Eu and Cm, for inter-metal competition studies regarding lanthanides and selected actinides and their binding to biological molecules.

In need of environmentally friendly methods for the separation and recycling of lanthanides and actinides, the binding of the protein lanmodulin to lanthanides and actinides was studied using time resolved laser induced fluorescence spectroscopy.