Polymeric copper(II) complexes with 4-formyl-3-methyl-1-phenylpyrazol-5-one hetarylhydrazones: Synthesis and crystal structures

4-Formyl-3-methyl-1-phenylpyrazol-5-one quinolin-2-yl-(H₂L¹) and benzothiazol-2-ylhydrazones (H₂L²) were synthesized and studied. Quantum-chemical modeling of possible tautomers of the hydrazones was performed. Copper(II) complexes of the general formula [Cu(HL)(ROH)]Y (R = CH₃, C₂H₅; Y=NO₃, ClO₄) were obtained and examined by IR and EPR spectroscopy, magnetochemistry, and X-ray diffraction. Additional coordination through the N atom of the pyrazole ring enables the complex molecules to form zigzag polymer chains linked by intermolecular hydrogen bonds.     

Synthesis of new spiropyranes and study of the effect of the nature of substituents on their photochromism and complexation

A series of new hydrazones based on 3,3-dimethyl-7-hydroxy-8-formyl-[2H]-1-benzopyran-2,1-[2]-oxaindane] with the substituents of different nature in the hydrazone moiety was synthesized. A comparative study of photochromism and complexation of the synthesized spiropyrans with a number of metal cations was carried out. Spectral and kinetic differences in photochromism and complexation of these compounds were revealed.     

EFFECT OF STRESSES ON POLYMER OXIDATION. QUANTITATIVE ASPECTS. III. KINETICS

Abstract

In the previous review cyclic molecules (model compounds) in reactions not involving ring opening and physical properties of stressed polymers were considered.     

Trends in formation of the nanocrystalline structure and cationic ordering in the Dy2O3-HfO2 (1: 1) system

Evolution of the nanocrystalline structure of the complex oxide Dy₂HfO₅ in the course of thermal annealing at temperatures to 1600°C has been studied by a combination of X-ray and synchrotron methods, including traditional and anomalous X-ray diffraction, PDF, EXAFS, and SAXS. The changes in crystallite size upon annealing of the as-synthesized amorphous precursor have been analyzed in detail. The systematic distortions of a fluorite-type perfect crystal structure (space group $Fm\bar 3m$ ) related to the nonequivalence of the local environment of the Dy and Hf cations but not resulting in formation of a pyrochlore-type cationordered structure in this system have been examined.     

Ellipsometric and IR spectroscopic study of the surface interaction of binary Al-REM alloys with water

The effect of Al-REM binary alloys’ composition on the kinetics of their surface oxidation by water is studied by means of ellipsometry and IR spectroscopy. Intermetallides with ～21 at % rare-earth metal in aluminum are oxidized in distilled water at 100°C, along with alloys of eutectic composition (Al-～2 at % REM) in solid and disperse state. It is found that the kinetic dependences of the thickness of films formed on pollycrystalline alloy samples and the IR transmission spectra of dispersed samples show that increasing the quantity of dopant REM in aluminum lowers the reactive capability of aluminum under certain conditions. It is found that the experimental ellipsometric results are described by a two-layer model consisting of a substrate, an inner oxide layer and an outer layer of hydroxide.     

Enumeration of non-labile oxygen atoms in dissolved organic matter by use of 16O/18O exchange and Fourier transform ion-cyclotron resonance mass spectrometry

We report a simple approach for enumeration of non-labile oxygen atoms in individual molecules of dissolved organic matter (DOM), using acid-catalyzed ¹⁶O/¹⁸O exchange and ultrahigh-resolution Fourier-transform ion-cyclotron-resonance mass spectrometry (FTICR-MS). We found that by dissolving DOM in H₂ ¹⁸O at 95 °C for 20 days it is possible to replace all oxygen atoms of DOM molecules (excluding oxygen from ether groups) with ¹⁸O. The number of exchanges in each molecule can be determined using high-resolution FTICR. Using the proposed method we identified the number of non-labile oxygen atoms in 231 molecules composing DOM. Also, using a previously developed hydrogen–deuterium (H/D)-exchange approach we identified the number of labile hydrogen atoms in 450 individual molecular formulas. In addition, we observed that several backbone hydrogen atoms can be exchanged for deuterium under acidic conditions. The method can be used for structural and chemical characterization of individual DOM molecules, comparing different DOM samples, and investigation of biological pathways of DOM in the environment.     

Synthesis of New Ursane-Type Hybrids with Morpholinomethyl-, Dialkylamino-, and Hydroxyl-Substituted Azoles

Chemistry of Natural Compounds - Ursane-type triterpenoids containing functionalized heterocyclic substituents were chemically modified. Aminomethylation of ursane hybrids with 1,3,4-oxadiazole-...