Formation of supported size-controlled nanoparticles of sulfated zirconia

Methods of the preparation of catalysts for alkane skeletal isomerization based on uniform nanoparticles of sulfated zirconia anchored to different supports were investigated. These catalysts were characterized by using the ICP, HRTEM and BET techniques. The activities of the catalysts in the reaction of n-butane isomerization were measured and compared with those of bulk catalysts.     

Adsorption thin-layer chromatography and viscometry of polystyrenes in solvent mixtures

The effect of the thermodynamic quality of solvent mixtures on the adsorption behavior of macromolecules under dynamic conditions was investigated. The chromatographic behavior of polystyrenes (PSs) in various mixed eluents was studied under conditions of adsorption and size-exclusion thin-layer chromatography as well as at the exclusion-adsorption transition point with silica gel KSKG adsorbent. The thermodynamic quality of the solvent mixtures used in the chromatographic experiments was determined viscometrically. The dependences of the intrinsic viscosity of PSs on solvent composition for solvent-non-solvent, two solvents, and theta-solvent-solvent mixtures were obtained. A correlation was found between Snyder's polarity indices for the solvent mixtures used in polymer chromatography under "critical conditions" and the intrinsic viscosity values of PSs in the same mixtures.     

Catalyzed Asymmetric Arylation Reactions

Addition and substitution reactions with carbon nucleophiles are fundamental processes in organic synthesis, and the development of general catalytic asymmetric variants thereof is still a major challenge today. In contrast to enantioselective alkyl transfer reactions, the corresponding arylations have not yet reached a high level of maturity. The existing protocols are either of no general applicability or are limited in terms of selectivity. This article summarizes established routes for catalytic asymmetric aryl transfer together with the latest developments in this area. The scope and limitations of this reaction are discussed.     

Preparation and redox properties of N,N,N-1,3,5-trialkylated flavin derivatives and their activity as redox catalysts

Eight different flavin derivatives have been synthesized and the electronic effects of substituents in various positions on the flavin redox chemistry were investigated. The redox potentials of the flavins, determined by cyclic voltammetry, correlated with their efficiency as catalysts in the H2O2 oxidation of methyl p-tolyl sulfide. Introduction of electron-withdrawing groups increased the stability of the reduced catalyst precursor.     

H-, C-NMR and ethylene polymerization studies of zirconocene/MAO catalysts: effect of the ligand structure on the formation of active intermediates and polymerization kinetics

Using ¹H- and ¹³C-NMR spectroscopies, cationic intermediates formed by activation of L₂ZrCl₂ with methylaluminoxane (MAO) in toluene were monitored at Al/Zr ratios from 50 to 1000 (L₂ are various cyclopentadienyl (Cp), indenyl (Ind) and fluorenyl (Flu) ligands). The following catalysts were studied: (Cp-R)₂ZrCl₂ (R=Me, 1,2-Me₂, 1,2,3-Me₃, 1,2,4-Me₃, Me₄, Me₅, n-Bu, t-Bu), rac-ethanediyl(Ind)₂ZrCl₂, rac-Me₂Si(Ind)₂ZrCl₂, rac-Me₂Si(1-Ind-2-Me)₂ZrCl₂, rac-ethanediyl(1-Ind-4,5,6,7-H₄)₂ZrCl₂, (Ind-2-Me)₂ZrCl₂, Me₂C(Cp)(Flu)ZrCl₂, Me₂C(Cp-3-Me)(Flu)ZrCl₂ and Me₂Si(Flu)₂ZrCl₂. Correlations between spectroscopic and ethene polymerization data for catalysts (Cp-R)₂ZrCl₂/MAO (R=H, Me, 1,2-Me₂, 1,2,3-Me₃, 1,2,4-Me₃, Me₄, Me₅, n-Bu, t-Bu) and rac-Me₂Si(Ind)₂ZrCl₂ were established. The catalysts (Cp-R)₂ZrCl₂/AlMe₃/CPh₃⁺B(C₆F₅)₄⁻ (R=Me, 1,2-Me₂, 1,2,3-Me₃, 1,2,4-Me₃, Me₄, n-Bu, t-Bu) were also studied for comparison of spectroscopic and polymerization data with MAO-based systems. Complexes of type (Cp-R)₂ZrMe⁺←Me⁻-Al≡MAO (IV) with different [Me-MAO]⁻ counteranions have been identified in the (Cp-R)₂ZrCl₂/MAO (R=n-Bu, t-Bu) systems at low Al/Zr ratios (50-200). At Al/Zr ratios of 500-1000, the complex [L₂Zr(μ-Me)₂AlMe₂]⁺[Me-MAO]⁻ (III) dominates in all MAO-based reaction systems studied. Ethene polymerization activity strongly depends on the Al/Zr ratio (Al/Zr=200-1000) for the systems (Cp-R)₂ZrCl₂/MAO (R=H, Me, n-Bu, t-Bu), while it is virtually constant in the same range of Al/Zr ratios for the catalytic systems (Cp-R)₂ZrCl₂/MAO (R=1,2-Me₂, 1,2,3-Me₃, 1,2,4-Me₃, Me₄) and rac-Me₂Si(Ind)₂ZrCl₂/MAO. The data obtained are interpreted on assumption that complex III is the main precursor of the active centers of polymerization in MAO-based systems.     

Theoretical analysis of the porphyrin-porphyrin exciton interaction in circular dichroism spectra of dimeric tetraarylporphyrins

Chiral bis-porphyrins are currently the subject of intense interest as chiral receptors and as probes in the determination of structure and stereochemistry. To provide an improved framework for interpreting the circular dichroism (CD) spectra of bis-porphyrins, we have calculated the CD spectra of chiral bis-porphyrins from three classes: I, where porphyrins can adopt a relatively wide range of orientations relative to each other; II, porphyrins have a fixed relative orientation; III, porphyrins undergo pi-stacking. The calculations primarily utilized the classical polarizability theory of DeVoe, but were supplemented by the quantum mechanical matrix method. Class I was represented by three isomers of the diester of 5alpha-cholestane-3,17-diol with 5-(4'-carboxyphenyl)-10,15,20-triphenylporphin (2-alphabeta, 2-betaalpha, 2-betabeta). Careful analysis of the torsional degrees of freedom led to two to four minimum-energy conformers for each isomer, in each of which the phenyl-porphyrin bonds had torsional angles near 90 degrees. Libration about these bonds is relatively unrestricted over a range of +/-45 degrees. CD spectra in the Soret region were calculated as Boltzmann-weighted averages over the low-energy conformers for each isomer. Three models were used: the effective transition moment model, in which only one of the degenerate Soret components is considered, along the 5-15 direction; the circular oscillator model, in which both Soret components are given equal weight; and the hybrid model, in which the 10-20 oscillator is given half the weight of the 5-15 oscillator, to mimic the effect of extensive librational averaging about the 5-15 direction. All three models predict Soret exciton couplets with signs in agreement with experiment. Quantitatively, the best results are given by the hybrid and circular oscillator models. These results validate the widely used effective transition moment model for qualitative assignments of bis-porphyrin chirality and thus permit application of the exciton chirality model. However, for quantitative studies, the circular oscillator or hybrid models should be used. The simplified effective transition moment and hybrid models are justified by the librational averaging in the class I bis-porphyrins and should only be used with such systems. Two class II bis-porphyrins were also studied by DeVoe method calculations in the circular oscillator model, which yielded good agreement with experiment. Class III bis-porphyrins were represented by 2-alphaalpha, for which the calculations gave qualitative agreement. However, limitations in the conformational analysis with the close contacts and dynamic effects in these pi-stacked systems preclude quantitative results.     

Novel Type of Tetranitrosyl Iron Salt: Synthesis,Structure and Antibacterial Activity of Complex [FeL’2(NO)2][FeL’L”(NO)2] with L’-thiobenzamide and L”-thiosulfate

In this work a new donor of nitric oxide (NO) with antibacterial properties, namely nitrosyl iron complex of [Fe(C₆H₅C-SNH₂)₂(NO)₂][Fe(C₆H₅C-SNH₂)(S₂O₃)(NO)₂] composition (complex I), has been synthesized and studied. Complex I was produced by the reduction of the aqueous solution of [Fe₂(S₂O₃)₂(NO)₂]²⁻ dianion by the thiosulfate, with the further treatment of the mixture by the acidified alcohol solution of thiobenzamide. Based on the structural study of I (X-ray analysis, quantum chemical calculations by NBO and QTAIM methods in the frame of DFT), the data were obtained on the presence of the NO…NO interactions, which stabilize the DNIC dimer in the solid phase. The conformation properties, electronic structure and free energies of complex I hydration were studied using B3LYP functional and the set of 6–31 + G(d,p) basis functions. The effect of an aquatic surrounding was taken into account in the frame of a polarized continuous model (PCM). The NO-donating activity of complex I was studied by the amperometry method using an “amiNO-700” sensor electrode of the “inNO Nitric Oxide Measuring System”. The antibacterial activity of I was studied on gram-negative (Escherichia coli) and gram-positive (Micrococcus luteus) bacteria. Cytotoxicity was studied using Vero cells. Complex I was found to exhibit antibacterial activity comparable to that of antibiotics, and moderate toxicity to Vero cells.     

Antihypothyroid Effect of Salidroside

In terms of prevalence, thyroid pathology, associated both with a violation of the gland function and changes in its structure, occupies one of the main places in clinical endocrinology. The problem of developing low-toxic and highly effective herbal preparations for the correction of thyroid hypofunction and its complications is urgent. Salidroside is a glucoside of tyrosol, found mostly in the roots of Rhodiola spp., and has various positive biological activities. The purpose of this study was to study the antihypothyroid potential of salidrosid-containing extract from R. semenovii roots, which was evaluated on a mercazolyl hypothyroidism model. We showed that extract containing salidroside is a safe and effective means of hypothyroidism correction, significantly reducing (p ≤ 0.001) the level of thyroid-stimulating hormone and increasing the level of thyroid hormones. The combined use of R. semenovii extract with potassium iodide enhances the therapeutic effect of the extract by 1.3-times.     

Optimization of the cathode porosity via mechanochemical synthesis with carbon black

Journal of Solid State Electrochemistry - Nanostructured carbon–coated composite cathode materials LiFe0.5Mn0.5PO4/C (LFMP/C) are prepared by the mechanochemically assisted solid-state...     

Design and Synthesis of Nitrogen-Rich Azo-Bridged Furoxanylazoles as High-Performance Energetic Materials

A series of novel energetic materials comprising of azo-bridged furoxanylazoles enriched with energetic functionalities was designed and synthesized. These high-energy materials were thoroughly characterized by IR and multinuclear NMR (¹H, ¹³C, ¹⁴N) spectroscopy, high-resolution mass spectrometry, elemental analysis, and differential scanning calorimetry (DSC). The molecular structures of representative amino and azo oxadiazole assemblies were additionally confirmed by single-crystal X-ray diffraction and X-ray powder diffraction. A comparison of contributions of explosophoric moieties into the density of energetic materials revealed that furoxan and 1,2,4-oxadiazole rings are the densest motifs while the substitution of the azide and amino fragments on the nitro and azo ones leads to an increase of the density. Azo bridged energetic materials have high nitrogen-oxygen contents (68.8–76.9 %) and high thermal stability. The synthesized compounds exhibit good experimental densities (1.62–1.88 g cm⁻³), very high enthalpies of formation (846–1720 kJ mol⁻¹), and, as a result, excellent detonation performance (detonation velocities 7.66–9.09 km s⁻¹ and detonation pressures 25.0–37.7 GPa). From the application perspective, the detonation parameters of azo oxadiazole assemblies exceed those of the benchmark explosive RDX, while a combination of high detonation performance and acceptable friction sensitivity of azo(1,2,4-triazolylfuroxan) make it a promising potential alternative to PETN.