On Global Classical Solutions of Hyperbolic Differential-Difference Equations

Doklady Mathematics - A one-parameter family of global solutions of a two-dimensional hyperbolic differential-difference equation with an operator acting with respect to a space variable is...     

Controlled ring‐opening homo‐ and copolymerization of ɛ‐caprolactone and d,l‐lactide by iminophenolate aluminum complexes: An efficient approach toward well‐defined macromonomers

The aluminum complexes containing two iminophenolate ligands of the type (p‐XC₆H₄NCHC₆H₄O‐o)₂AlR' (R′=Me ( 3, 4 ) or R′=O(CH₂)₄OCH=CH₂ ( 5, 6 ), X=H ( 3, 5 ), F( 4, 6 )) were synthesized and characterized by ¹H, ¹³C NMR spectroscopy, and X‐ray crystallography. The reaction of AlMe₃ with two equivalents of substituted iminophenols gave five‐coordinated {ONR}₂AlMe ( 3, 4 ) complexes. Subsequent reaction of these methyl complexes with unsaturated alcohol, HO(CH₂)₄OCH=CH₂, resulted in target compounds 5 and 6 in a good yield. It was shown that the complexes ( 3 ‐ 6 ) are monomeric in solution (NMR) and in solid state (X‐ray analysis). The catalytic activity of the complexes 5 and 6 towards ring‐opening polymerization (ROP) of ?‐caprolactone and d,l ‐lactide was assessed. Complex 5 showed higher activity as compared with 6 , while both of these catalysts induced controlled homo‐ and copolymerization to afford the macromonomers with high content of vinyl ether end groups (F_n > 80%) in a broad range of molecular weights (M_n = 4000–30,000 g mol^?1) with relatively narrow MWD (M_w/M_n = 1.1–1.5). © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1237–1250     

Phase transitions in crystals of protein amino acids with trapped drops of water solutions

It has been shown that the phase transitions observed at temperatures of about 250 K in crystals of protein amino acids and of their compounds grown from water solutions are related to drops of these solutions trapped by crystals in their growth.     

Manufacture of Magnesium Oxide Nanoparticles Coated with Silica Shells

MgO@SiO₂ core–shell nanoparticles were manufactured, and a synthetic protocol was developed to prepare MgO nanoparticles where the SiO₂ shell thickness was less than 10 nm. The influence of synthesis parameters on the formation of MgO@SiO₂ nanoparticles was studied. The fact of a SiO₂ shell being formed on the MgO surface was established and the sizes of the thus-prepared MgO@SiO₂ nanoparticles were determined by TEM and Fourier-transform IR spectroscopy.     

Catalysts based on filamentous carbon in the hydrogenation of aromatic compounds

In order to extend the area of application of the base catalytic system metal-filamentous carbon, the catalytic properties of Ni-filamentous carbon catalysts have been tested in the hydrogenation of aromatic compounds (benzene, benzyl cyanide, benzophenone, and nitrobenzene). The selectivity of the catalysts depends on the outer faceting of the active metal particles. The benzene ring is hydrogenated on the (111) face of the metal nanoparticles, whereas the selective hydrogenation of functional groups in substituted aromatic compounds occurs on the surface of active component nanoparticles in which the (111) face is blocked.     

Ytterbium tris(hexafluoroacetylacetonate) Yb(C<Subscript>5</Subscript>O<Subscript>2</Subscript>HF<Subscript>6</Subscript>)<Subscript>3</Subscript>: The composition of overheated vapor and sublimation thermodynamics

A mass spectrometric study of the saturated vapor over ytterbium tris(hexafluoroacetylacetonate) Yb(hfa)₃ (hfa = CF₃-C(O)-CH-C(O)-CF₃) and of the vapor overheated up to the thermal decomposition temperature of the complex is presented. The vapor composition changes markedly with increasing temperature. At T ≈ 370 K, the mass spectrum of the vapor over Yb(hfa)₃ indicates the presence of ions containing one to three metal atoms. As the temperature is raised, the ion currents due to oligomer ions decrease. The oligomers are not detected at T > 440 K. The total decomposition temperature of Yb(hfa)₃ is 663(9) K. The second-law enthalpy of sublimation (ΔH _s^o (380 K)) is 134 ± 7 kJ/mol for the monomer and 138 ± 10 kJ/mol for the dimer. The enthalpy of dissociation of the dimer into monomer molecules is nearly equal to the enthalpy of sublimation of the monomer and dimer: ΔH _dis(380 K) = 130 ± 15 kJ/mol.     

The Interaction of Maleic Anhydride,N -Vinylpyrrolidone,and Their Mixture with 2,2-Diphenyl-1-picrylhydrazyl

Spectrophotometry studies have shown that N-vinylpyrrolidone and/or maleic anhydride interact with 2,2-diphenyl-1-picrylhydrazyl radical in a solution. Thermochemical parameters of the most probable reactions involving these compounds have been estimated by means of the PM6 and B3LYP/6-31+G(d) (gas phase) density functional theory methods. It has been suggested that the stable radical is attached to the monomer molecule, the resulting radical being involved in the chain growth reactions. Termination via the oligomeric radicals recombination is the most probable.     

Ion-molecular interactions in the metalloporphyrin-acid system in liquid solutions

A new form of MP...H _solv ⁺ metalloporphyrins is found and studied in the strong acid medium, the conditions of its formation and the qualitative reaction of its determination are established. It is shown that the same form has the H₄TPP²⁺ dication (TPP is the 5,10,15,20-tetraphenyl-21H,23H-porphyrine dianion). The stability in different acid media and in the isolated state, spectral properties and the structure of H⁺-associates of porphyrins are analyzed in detail by UV-visible and ¹H NMR spectroscopy and quantum chemical calculations. It is shown that they have a unique two-band visible electronic spectrum with the bands near 540 nm and 700 nm, which weakly depend on the type of the central atom in the complex and noticeably change when the chromophore is functionally substituted. The proton location the ion-molecular associate and the cases of the formation of H⁺-associates with higher stoichiometry are revealed.     

Mechanism of the oxidation of ferrocene and its derivatives with hydrogen peroxide: A new effect

A new effect was recorded during the studies of the mechanism of ferrocene oxidation with hydrogen peroxide, namely, a shift of λ_max of the absorption band of the ferricinium cation (ABFC) toward the long-wave region and its broadening during the reaction. The shiftΔλ_max increased with the excess of the H₂O₂ concentration with respect to the ferrocene concentration and reached 90 nm and more at H₂O₂/Fc ≈ 80–100. Similar changes in ABFC took place during the oxidation of a series of ferrocene derivatives. A shift of ABFC was not revealed at comparable concentrations of the metal complex and H₂O₂. During the oxidation of ferrocene with other peroxides (t-C₄H₉OOH or (PhCOO)₂), there were no changes in the spectrum of the ferricinium cation at any ratios of reagent concentrations. The observed effect is based on the formation of a {ferricinium cation + ^.OH} radical pair during the primary interaction of the metallocomplex with H₂O₂ and subsequent reaction between the radicals of the radical pair according to the radical substitution mechanism, which leads to the formation of the hydroxy derivatives of ferrocene and their cations. Sequential accumulation of OH substituents in the metallocomplex and the corresponding ferricinium cations caused a continuous shift of ABFC toward the long-wave region.     

Synthesis,structure, and reactivity of germanium-containing derivatives of substituted diethanolamines

The reaction of dialkanolamines RN(CH₂CH₂O)(CHR’CHR’OH) (R = Me, Ph, PhCH₂; R’ = H, Ph) with tetraethoxygermane gives either 2,2-diethoxy-1,3,6,2-dioxazagermocanes RN(CH₂CH₂O)(CHR’CHR’O)Ge(OEt)₂ or 1,7,9,15-tetraoxa-4,12-diaza-8-germaspiro[7.7]pentadecanes [RN(CH₂CH₂O) (CHR’CHR’O)]₂Ge depending on the reactant ratio. The chemical behavior of the obtained compounds in substitution reactions at germanium was studied. The product structure was confirmed by elemental analysis data and ¹H, ¹³C, and ¹⁹F NMR spectroscopy. The cyclotrigermanoxane [MeN(CH₂CH₂O)₂GeO]₃ was studied by X-ray diffraction.