Synthesis of an inorganic-organic polymer blend from orthoboric acid and caprolactam

The possibility of modifying boron polyoxide with an oligomeric amide upon thermal dehydration of orthoboric acid and oligomerization of caprolactam in a common melt is shown. The products obtained after thermal pretreatment of the initial blend containing 30 wt % caprolactam are investigated. It is shown that the main processes at T < 200°C are dehydration of orthoboric acid and hydrolysis of caprolactam with the formation of ε-aminocaproic acid. At temperatures of 225–260°C, the predominant process is the formation of boron polyoxide and a caprolactam-based oligomeric product. The data of ¹¹B NMR spectroscopy show that the chemical transformations of caprolactam occur against the background of the N:B donor-acceptor interaction. The two-dimensional [¹¹B-¹H] heteronuclear correlation spectrum indicates that the systems obtained upon thermal treatment are solid solutions.     

Changes in the structural parameters and molecular dynamics of polyhydroxybutyrate-chitosan mixed compositions under external influences

Differential scanning calorimetry (DSC), EPR probe analysis, large-angle X-ray diffraction (XRD), and UV spectroscopy are used to study the molecular dynamics and structure of hydroxybutyrate (PHB) copolymer, chitosan, and mixed compositions thereof upon thermal treatment in an aquatic medium. It is shown that, in mixed compositions, starting from 30% PHB, the correlation time increases by an order of magnitude, indicative of a sharp slowdown of the molecular mobility of the probe, and, concurrently, the degree of crystallinity decreases abruptly, as evidenced by DSC and XRD analyses. The diffusion coefficient of rifampicin in mixed compositions also decreases with increasing PHB content. A short-term (1 h) thermal treatment (at 70°C) in water results in an increase in the molecular mobility of the probe in the system. Crystallinity changes in complex ways.     

Features of stable radical generation in lignin on exposure to nitrogen dioxide

The mechanism of stable radical generation in lignin under the action of nitrogen dioxide and NO₂ - air mixture is considered. The formation of phenoxyl, iminoxyl and acylaminoxyl radicals has been detected by EPR. The proposed mechanism involves a primary oxidative reaction of phenol groups with dimers of NO₂ (nitrosyl nitrate) resulting in the formation of phenoxyl radicals and nitric oxide. In the subsequent recombination of phenoxyl radicals and nitric oxide, nitroso compounds and oximes are formed. By reaction of oximes with radicals NO₂, stable iminoxyl radicals are formed. This mechanism is confirmed by kinetic dependencies obtained over a wide range of NO₂ concentrations. From IR spectroscopy measurements it follows that hydroxyl groups of non-phenolic structures of lignin are oxidised to aldehydes producing acylaminoxyl radicals by reaction with NO₂. The kinetic data show that the adsorption of NO₂ on the lignin surface is the rate-determining factor in stable radical formation.     

Plasma oscillations in fullerene molecules within the random phase approximation

A method is presented for calculating the density of plasma excitation modes in fullerene molecules, which makes it possible to describe more accurately the specific features of the spectra as compared to the models proposed previously. The method is based on the inclusion of the total contribution of π and σ electrons to the spectra of collective oscillations in the molecules. This allows one to consider fullerene molecules with an arbitrary symmetry and arbitrary substituents. A comparative analysis of the experimental curves obtained for resonance electron capture and the results of numerical simulations for C₆₀, C₇₀, and C₇₆ molecules has demonstrated that not only the main maxima but also the ranges of the formation of negative ions coincide.     

Calculation of the thermodynamic properties of the dimethacrylate esters of aliphatic glycols

Russian Chemical Bulletin -