Synthesis and psychotropic properties of furyl- and thienyl-germatranes

Trihalogermyl-furans and -thiophenes were prepared by inserting germanium dibromide (GeBr₂) generated from the dibromogermane(II) dioxanate complex into the carbon-halogen bond of halo-furans and -thiophenes. Their ethanolysis and transesterification by triethanolamine yielded the germatranes which were subjected to psychotropic activity assays. The psychotropic properties of germatranes were found to depend on the type of the heterocycle and on the position of the germatrane moiety.     

Intramolecular Dynamics and Molecular Structure of Europium(III) Chelate Complexes with Crown Ethers as Studied by NMR Spectroscopy

Earlier the intramolecular inversion of the 18-crown-6 molecules was found in the complex ion pairs [Ln(ptfa)₂ (18-crown-6)]⁺ [Ln(ptfa)₄]⁻ (H₂O)₄ where Ln = La(1), Ce (2), Pr (3), Nd (4), and ptfa is 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione. In this work the peculiarities of the molecular structure and dynamics were studied for [Eu(ptfa)₂ (18-crown-6)]⁺ [Eu(ptfa)₄]⁻ (H₂O)₄ (5) by NMR spectroscopy techniques. Through VT-NMR spectra analysis the temperature dependence was obtained for the rate constant. The free energy ΔG^‡(320) of 18-crown-6 ring inversion activation was found to be 65 ± 5 kJ mol⁻¹ for 5 in CDCl₃. This result is comparable with the earlier data [S.P. Babailov and D.A. Mainichev: J. Inclusion Phenom. Macrocyclic Chem. 43, 187–193 (2002)] for complexes 2, 3, 4 in deuterated toluene (ΔG^‡(320)=65 ± 9, 64 ± 9, 64 ± 9 kJ mol⁻¹ respectively). It was found by relaxation NMR spectroscopy that the effective distance between Ln and protons of the crown molecule is 4.5 ± 0.2 Å. The analysis of structural parameters testifies that the crown ether and chelated anions are in the first coordination sphere of a Ln cation. Obtained geometrical parameters show that the complex cations of Eu, Ce and Pr have similar spatial structures.This revised version was published online in July 2005 with a corrected issue number.     

NMR Studies of Mixed-Ligand Lanthanide Complexes in Solution: Pseudorotation and Ring Inversion of 18-Crown-6 Molecule in Cerium Subgroup Chelates

¹H and ¹³C NMR measurements are reported for the CDCl₃ and CD₂Cl₂ solutions of [La(NO₃)₃(18-crown-6)] (I), [Pr(NO₃)₃(18-crown-6)] (II) and [Ce(NO₃)₃(18-crown-6)] (III) complexes. Temperature dependencies of the ¹H NMR spectra of II have been analyzed using the dynamic NMR methods for multi-site exchange. Two types of conformational dynamic processes in II were identified (the first one with activation enthalpy ΔH ^‡=26 ± 4 kJ/mol is conditioned by interconversion of complex enantiomeric form and pseudorotation of macrocycle molecule upon the C ₂ symmetry axis, the second one with ΔH ^‡=46 ± 5 kJ/mol is conditioned by macrocycle molecule inversion). Studies of the values of the lanthanide-induced shifts revealed that the structure of complexes in solution is similar to that reported for the complex I in the crystal state.This revised version was published online in July 2005 with a corrected issue number.     

Calcium Phosphate Dental Materials Prodused with the Help of Natural Alumosilicates

Abstract

Calcium phosphates are well known to be perspective as biomaterials, for example. the dental ones. There are two tendencies in investigation and design of such materials. They are the search of porous biomaterials and development of dense bioceramics on the basic of hydroxópatite and crystallized calcium phosphate glasses. Control of glasses crystallization with the help of modificators and nucleating agents is the main way for producing dense biomaterials [1, 2]. We used natural alumosiiicates, for example, kaolin as a reagent and modificator for calcium polyphosphate to achieve a good quality of materials without stages of glass formation and glass crystallization.     

Inequalities for Purity Parameters of Multiqudit and Single-Qudit States

We analyze the recently found inequality for eigenvalues of the density matrix and purity parameters describing either a bipartite-system state or a single-qudit state. We rewrite the Minkowski-type trace inequality for the density matrices of the qudit states in terms of the purity parameters and discuss the properties of the inequality obtained, paying special attention to the X-states of two qubits and a single qudit. Also we study the relation of the purity inequalities obtained with the entanglement.     

Combining electrophoresis with detection under ultraviolet light and multiple ultrafiltration for isolation of humic fluorescence fractions

Polyacrylamide gel electrophoresis of chernozem soil humic acids (HAs) followed by observation under UV (312 nm) excitation light reveals new low molecular weight (MW) fluorescent fractions. Ultrafiltration of HAs sample in 7 M urea on a membrane of low nominal MW retention (NMWR, 5 kDa) was repetitively used for separation of fluorescent and non-fluorescent species. Thirty ultrafiltrates and the final retentate R were obtained. Fluorescence maxima of separate ultrafiltrates were different and non-monotonously changed in the range of 475–505 nm. Fluorescence maxima of less than 490 nm were detected only in the four first utrafiltrates. For further physical–chemical analyses all utrafiltrates were combined into a fraction called UF < 5 (NMW < 5 kDa). Retentate R demonstrated very weak fluorescence under 270 nm excitation, while fluorescence intensity of UF < 5 was about six times higher than of the bulk HAs. Fraction UF < 5 was further ultrafiltrated on membranes of MNWR 3 kDa and 1 kDa, yielding three subfractions UF3-5, UF1-3 and UF < 1 with NMW 3–5 kDa, 1–3 kDa and <1 kDa, respectively. The validation of the UF procedure was performed by size exclusion chromatography on Sephadex G-25 column. The fluorescence maxima were found to be at 505, 488 and 465 nm for UF3-5, UF1-3 and UF < 1, respectively, with increasing of fluorescence intensity from UF3-5 to UF1-3 to UF < 1 fraction. EPR analysis showed that the amount of free radicals was the largest in retentate R and drastically decreased in fluorescent ultrafiltrates. The results demonstrate that more than one fluorophore is present in chernozem soil HAs complex.     

Magnetooptical activity of spinel type crystals with complex mixed-valence lattice irregularities

In this Letter we analyze the peculiarities of the Faraday rotation in the imperfect spinel type crystals for which the lattice irregularities are represented by the mixed valence clusters of transition metal ions. A such kind of complex system with the electronic configuration (for example, Mn2+Mn2+Mn3+) is considered in detail. The model takes into account the cubic and low symmetry crystal fields acting on the metal ions, migration of the “extra” hole as well as the orientational degeneracy (hidden optical anisotropy). The electric dipole transitions in these types of clusters with migrating hole coupled to the spin core through the double exchange mechanism are shown to lead to a significant magnetooptical activity in the visible range of spectrum. The intensity of these transitions can be comparable or higher than those for the magnetic dipole ones in the same range of frequencies. The electric dipole mechanism of the magnetooptical effects manifests itself in a highly anisotropic character of the spectra.     

Solvent Effect on the Enthalpy of Solution and Partial Molar Volume of the Ionic Liquid 1-Butyl-3-methylimidazolium Tetrafluoroborate

Enthalpies of solution and partial molar volumes of the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate were determined in 15 solvents of different polarity. Very large differences of the enthalpies of solution (????_sol H _IL=38.9?kJ?mol^?1) and partial molar volumes (??V _IL=43 cm³?mol^?1) are nearly the same as observed for lithium perchlorate solutions. These results clearly indicate that the low values of the macroscopic polarity parameters of [bmim]BF₄ do not correspond with the large differences of the intermolecular interactions in IL solutions. The values of the partial molar volume of the cation, $V_{[\mathrm{bmim}]^{+}}$ , were estimated for the first time. The changes of the partial molar volumes, V _IL, reflect mainly the changes of anion volume, $V_{\mathrm{BF}_{4}^{-}}$ . The rate of the Diels?CAlder reaction of 9,10-dimethylanthracene with maleic anhydride in the [bmim]BF₄ medium was nearly the same as in common molecular solvents.