Vol 479, No 2 (2018)
- Year: 2018
- Articles: 8
- URL: https://journals.rcsi.science/0012-5008/issue/view/9290
Chemistry
Synthesis of Nanotitania on the Surface of Titanium Metal in Ionic Liquids: Role of Water Additions
Abstract
The anodic oxidation of a titanium metal electrode in two ionic liquids was studied of amorphous titania nanostructures were obtained. The nanostructures are formed only in the case where a hydrophilic ionic liquid (1-butyl-3-methylimidazolium chloride) with addition of some water is used as the electrolyte. The role of water is to provide a sort of construction material (source of oxygen) for titania nanostructures. In the hydrophobic ionic liquid (1-butyl-3-methylimidazolium), the thickness of the anodic oxide increases and no nanostructures are formed.
New Vanadium Germanium Garnets
Abstract
New vanadatogermanates Ca3–xMe2 + xV2GeO12, Ca3Mе2VGe2O12, and Ca3Me2Ge3O12, where Me = Mg, Mn, Co, Ni, Fe, Zn, and x = 0–1, have been synthesized through coupled substitutions of cations in the initial garnets Ca2.5Mn2V3O12 or Ca3Fe2Ge3O12. The unit cell parameters of the synthesized samples have been determined. Probability analysis of the cation distribution in the octahedral positions of the crystal lattice as a function of crystallographic radii has been performed taking into account the spin state of the cations.
Addition Polymerization of 5-Ethylidene-2-Norbornene in the Presence of Pd N-Heterocyclic Carbene Complexes
Abstract
New high-performance catalytic systems based on Pd N-heterocyclic carbene complexes for the selective addition polymerization of 5-ethylidene-2-norbornene (ENB) were proposed. With these catalysts, polymerization can be conducted at unprecedentedly high monomer/catalyst ratio (up to 5 × 105/1) and gives high-molecular-weight soluble polymers with good film-forming properties. Varying the polymerization conditions (reaction temperature, monomer and catalyst concentrations, monomer/Pd ratio) makes it possible to prepare soluble ENB-based addition polymers with specified molecular weights in reasonable yields.
Reversible Migrations of Nitro Group in a Methyltetramethoxycarbonylcyclopentadiene System
Abstract
Quantum chemical calculations by the density functional theory method at the B3LYP/6-311++G** level have shown that 5-nitro-5-methyl-1,2,3,4-tetramethoxycarbonylcyclopentadiene (1) and 5-nitro-2-methyl- 1,3,4,5-tetramethoxycarbonylcyclopentadiene (2) undergo interconversion by consecutive 1,5-sigmatropic shifts via the formation of an unstable isomer, 5-nitro-1-methyl-2,3,4,5- tetramethoxycarbonylcyclopentadiene (3), rather than through the NMR-detected 1,3-shift of the nitro group over the cyclopentadiene ring perimeter. According to calculations in the gas phase, isomer 3 is by ΔEZPE of 3.6 kcal/mol less stable than isomer 1, while the activation barrier of the stepwise 1 → 2 process is 24.5 kcal/mol, which agrees well with NMR data (ΔG25C≠, chlorobenzene, 26.5 kcal/mol).
Effect of the Chemical Structure of Heat-Resistant Thermoplastics on the Friction on Steel
Abstract
A general approach to understanding the complex nature of the friction of friction-resistant heatresistant thermoplastics has been developed. This approach made it possible to idenify two main factors determining the basic character of the friction of these polymers on steel: the dispersion component of the intermolecular interaction energy and the molecular weight. Specific properties of some polymers can be used to refine the friction behavior.
Synthesis of Tetraazide Derivatives of p-tert-Butylcalix[4]arene Using Copper-Catalyzed Nucleophilic Aromatic Substitution
Abstract
Aromatic azido derivatives of p-tert-butylcalix[4]arene have been obtained for the first time using copper-catalyzed nucleophilic aromatic substitution of azide anion for bromide in 5,11,17,23-tetrabromo- 25,26,27,28-tetrabuthoxycalix[4]arene in a dioxane–water (3: 1) solvent mixture with N,N-dimethylethylenediamine as a stabilizing ligand for copper(I). When the reaction is carried out under with microwave heating, partial substitution products (mono-, distally di-, proximally di-, and trisubstituted) can be isolated in satisfactory yields.
Chemical Technology
Overall Kinetics of Heat Treatment of Municipal Solid Waste
Abstract
A mathematical model of the overall kinetics of heat treatment of municipal solid waste was developed. The model considers the main initial substances and products of the reaction of municipal solid waste treatment at high temperatures (1300–1500°C) in a tubular flow reactor.
Methodology for Developing a Specialized Ontology for Chemical Technology of Reagents and Special-Purity Substances
Abstract
Two methodologies for developing a specialized ontology for chemical technology of reagents and special-purity substances were proposed. One of them is a methodology for developing the structure and conceptual content of a specialized ontology for the chemistry and technology of production of reagents and special- purity substances. The other is a methodology for using the specialized ontology in interactive intelligent systems for semantic processing of science and technology texts.