Stereochemistry of Seven-membered Heterocycles: XLIV. Spatial Structure of 4-R-3,5-Dioxabicyclo[5.1.0]octanes

4-R-3,5-Dioxabicyclo[5.1.0]octanes were prepared in good yields by reduction of the corresponding 8,8-dichloro derivatives in a system Li-t-BuOH. According to the data of dynamic ¹H and ¹³CNMR spectroscopy involving experiments in the NOESY mode the formal (R = H) at −93°C in (CD₃)₂CO exists in nearly equally occupied chair forms with endo- and exo-oriented three-membered ring. The like structure were found in the diastereomeric 4-Me(t-Bu)-analogs. The characteristic feature of ¹³C NMR spectra consists in considerable difference in the chemical shifts of the C⁸ atoms (Δδ∼16–17 ppm). The data on epimerization of diastereomers and calculations along AM1 procedure suggest for formal a three-component equilibrium including a twist-form.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 2, 2005, pp. 301–305.Original Russian Text Copyright © 2005 by Fedorenko, Baryshnikov, Khairutdinov, Vafina, Shtyrlin, Klochkov, Klimovitskii.     

Reactions of heteroaromatic chromophores with lanthanide complexes of p-sulfonatothiacalix[4]arene

The conditions for the formation of heteroleptic complexes of a lanthanide(iii) ion (Ln = La, Gd, and Tb) with p-sulfonatothiacalix[4]arene and a heteroaromatic chromophore in water were found using X-ray diffraction analysis, pH-metry, ¹H NMR and UV—Vis spectroscopy, and nuclear magnetic relaxation. In the resulting complexes, the heteroaromatic chromophore is in the calix[4]arene cavity and the lanthanide ion is coordinated by the electron-donating groups of the upper or lower calix[4]arene rim. Emission spectroscopic studies revealed changed emission properties of Tb^III ions in the terbium(iii)—p-sulfonatothiacalix[4]arene—bipy complex. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1871–1878, September, 2008.     

Generation of new landomycins by combinatorial biosynthetic manipulation of the LndGT4 gene of the landomycin E cluster in S. globisporus

A 3 kb DNA fragment from the Streptomyces globisporus 1912 landomycin E (LaE) biosynthetic gene cluster (lnd) was completely sequenced. Three open reading frames were identified, lndGT4, lndZ4, and lndZ5, whose probable translation products resemble a glycosyltransferase, a reductase, and a hydroxylase, respectively. Studies of generated mutants from disruption and complementation experiments involving the lndGT4 gene allowed us to determine that LndGT4 controls the terminal L-rhodinose sugar attachment during LaE biosynthesis and that LndZ4/LndZ5 are responsible for the unique C11-hydroxylation of the landomycins. Generation of the novel landomycins F, G, and H in the course of these studies provided evidence for the flexibility of lnd glycosyltransferases toward their acceptor substrates and a basis for initial structure-activity relationships within the landomycin family of antibiotics.     

Dilute-and-shoot approach for determination of several biomarkers and pharmaceuticals in wastewater using nanoflow liquid chromatography – Orbitrap mass spectrometry

A new method for quantitative analysis of several biomarkers and pharmaceutical compounds in wastewater has been developed employing nanoflow liquid chromatography with Orbitrap mass spectrometry. An easy dilute-and-shoot approach has been used for sample preparation with a dilution factor of 5. Improved retention of ionic and highly polar compounds has been achieved by the addition of tetrabutylammonium bromide as an ion pair reagent into the final diluted sample. The new nanoflow liquid chromatography method has demonstrated low matrix effects (70%–111%), high sensitivity in terms of limits of quantification (0.005 to 0.3 μg/L), low injection volume (70 nl) and solvent consumption, and the ability to analyze diverse polar and ionic analytes within one run using a single reversed-phase nanoflow liquid chromatography column. Wastewater samples (n = 116) from the wastewater treatment plants of different cities in Latvia were analyzed using the developed method. The observed concentrations of biomarkers were in line with the literature data.     

XPS spectra of vanadium-doped disulfides CuCrS<Subscript>2</Subscript>

The charged state of atoms in layered cation-substituted disulfides CuCr_1?x V _x S₂ (x = 0?0.4) was studied using X-ray photoelectron spectroscopy. The study was performed with polycrystalline powder and ceramic samples of chromium-copper disulfides. CuCr_1?x V _x S₂ samples were shown to comprise differently charged atoms of chromium, copper and vanadium, the charged state of which varies with the concentration of vanadium cations (x).     

Optical properties of a new photorecording polymer based on 2,2-difluoro-4-(9-anthracyl)-6-methyl-1,3,2-dioxaborine

The optical properties of a new photorecording polymer based on 2,2-difluoro-4-(9-anthracyl)-6-methyl-1,3,2-dioxaborine have been investigated. This material is found to change its absorption coefficient and refractive index in the visible range under illumination with a wavelength λ = 405.9 nm. This circumstance makes it possible to record static holograms with a spatial frequency up to 2500 lines/mm, a diffraction efficiency above 60%, and a lifetime more than 6 months. A dynamic change in the effective refractive index of this material under 405.9-nm irradiation is found, due to which one can form control optical elements of the light-light type with a modulation frequency up to 50 Hz in it.     

Resource-saving electrochemical processes in manufacture of pigment titanium dioxide

Development directions of the sulfate method for manufacture of titanium dioxide are considered, and alternative solutions for improving its cost efficiency and ecological advisability are suggested. A high-efficiency technology for electrochemical synthesis of a strong reducing agent, Ti₂(SO₄)₃·nH₂O, used instead of waste iron and powdered aluminum is suggested.     

CRYSTAL STRUCTURE AND X-RAY CRYSTALLOGRAPHIC ANALYSIS OF THE BINUCLEAR CLUSTER THIOCYANATE COMPLEX OF NIOBIUM(IV)

Journal of Structural Chemistry - The structure of a binuclear niobium(IV) thiocyanate complex (Bu4N)4[Nb2(μ2-S2)2(NCS)8]·H2O (1·H2O) is studied by X-ray crystallography. Compound...